Polyurethane Thickeners

ABSTRACT

The present invention relates to a process for preparing polyurethanes, which comprise at least three hydrophilic sections, at least four hydrophobic sections, optionally allophanate segments and/or isocyanurate segments and which are prepared in the presence of alkali(ne earth) metal carboxylates. The process may comprise using at least one carboxylic acid salt of at least one metal selected from the group consisting of the alkali metals, the alkaline earth metals and mixtures thereof. Furthermore, the present invention relates to the polyurethanes per se obtainable in this way, to the use thereof as thickeners for aqueous preparations, and to preparations comprising polyurethanes of this type.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims priority under 35 U.S.C. §119(e) to U.S.Provisional Application No. 61/405,653, filed on Oct. 22, 2010, which isincorporated herein by reference in its entirety.

FIELD

The present invention pertains to polyurtheranes, preparationscomprising polyurethanes, the use of polyurethanes as thickeners foraqueous preparations and processes for preparing polyurethanes.

BACKGROUND

Polyurethanes have been used for a long time in numerous fields ofapplication for highly diverse purposes. Depending on the choice ofstarting materials and the stoichiometric ratio of the startingmaterials, polyurethanes are obtained with very differentphysicochemical properties.

Thickeners are used widely for increasing the viscosity of aqueouspreparations, for example in the fields of cosmetics, human and animalnutrition, pharmacy and for detergents, paints and coatings. Inter alia,polyurethanes are also known as thickeners.

For example, polyurethane solutions or dispersions in water-dilutableaqueous or predominantly aqueous phase are referred to by the personskilled in the art as HEUR thickeners (“hydrophobically modifiedethylene oxide urethane copolymer”), and have already been used for arelatively long time in highly diverse fields of application, forexample for thickening water-based emulsion paints.

The action principle of the thickening effect of the HEUR thickeners inthe afore-mentioned example is assumed to be that the polyethyleneglycol segments ensure the water compatibility and the hydrophobicsegments construct a viscosity-imparting three-dimensional molecularassociation via an association with one another and also with dispersedbinder particles of the emulsion paint to be thickened therein.

Thickeners are also used in the field of cosmetic preparations.Thickeners for cosmetic preparations are expected to have an adequatethickening effect even in preparations with a high content of salt.Furthermore, such thickeners should produce cosmetic preparations with agood texture and pleasant feel on the skin. Compatibility with numerousother auxiliaries, in particular with salts and surfactants, and alsoincorporability of the thickener itself and also of the otherauxiliaries should be provided.

Moreover, the thickened preparations must have constant rheology andphysical and chemical quality even upon long-term storage, and in thecase of changes in temperature and pH. Finally, it should also bepossible to produce these thickeners in a cost-effective manner andwithout a notable impact on the environment.

U.S. Pat. No. 4,079,028 and U.S. Pat. No. 4,155,892 disclose, interalia, linear polyurethane thickeners. The preparation of thepolyurethanes specified therein is catalyzed by the catalyst dibutyltindilaurate (DBTL) customary in polyurethane chemistry.

EP 1584331 and EP 1013264 describe polyurethane thickeners for cosmeticpreparations. These are prepared in a single-step process by reactionwithout a diluent from polyol, polyisocyanate and fatty alcohol, whichmay be ethoxylated if desired, and without use of a catalyst.

WO 2006/002813 describes polyurethane thickeners for variousapplications in aqueous media. These thickeners are prepared fromhydrophilic polyols having at least two hydroxy groups, one or morehydrophobic compounds, e.g. long-chain alcohols, and at leastdifunctional isocyanates. Here, an excess of NCO groups is used. Thecatalyst used is 1,8-diazabicyclo-[5-4-0]undec-7-ene (DABCO).

WO 02/88212 describes polyurethanes of ethoxylated long-chain alcoholsand cyclic diisocyanate oligomers, for example isocyanurates, asstarting materials. The polyurethanes described are prepared withoutusing a catalyst.

EP 725097 describes polyurethane thickeners, during the preparation ofwhich polyethers, produced by alkoxylation of alcohols or alkylphenols,are reacted with polyisocyanates with catalysis by DBTL,diazabicyclooctane or tin dioctoate, the ratio of NCO to OH equivalentsbeing in the range from 0.9:1 to 1.2:1. These thickeners are proposedfor use in the field of low shear forces, e.g. for the flow ofwater-based emulsion paints.

EP 1241198, EP 1241199, and EP 1241200 describe the preparation ofpolyurethane thickeners with DBTL catalysis and use of polyetherpolyolsand urethane-group-containing polyetherpolyols with functionalities >2(for example ethoxylated sugars, glycerol, etc.).

EP 761780 and EP 1111014 describe polyurethane thickeners composed ofpolyethylene glycol, diisocyanate and branched, preferablylong-chain-branched alkyl groups as hydrophobic component. Thepreparation takes place in the melt without using a catalyst.

WO 2009/135856 and WO 2009/135857 describe water-dispersiblepolyurethanes with an essentially linear backbone composed ofalternating hydrophilic and hydrophobic sections and uses thereof. Thepolyurethane formation is catalyzed by titanium or zinc compounds.

SUMMARY

Embodiments of the present invention relate to a process for preparingpolyurethanes which comprise at least three hydrophilic sections, atleast four hydrophobic sections, optionally allophanate segments and/orisocyanurate segments and which are prepared in the presence ofalkali(ne earth) metal carboxylates.

Further embodiments of the present invention relate to the polyurethanesper se, obtainable in this way, to the use thereof as thickeners foraqueous preparations, and to preparations comprising polyurethanes ofthis type.

BRIEF DESCRIPTION OF THE DRAWING

So that the manner in which the above recited features of the presentinvention can be understood in detail, a more particular description ofthe invention, briefly summarized above, may be had by reference toembodiments, some of which are illustrated in the appended figures. Itis to be noted, however, that the appended figures illustrate onlytypical embodiments of this invention and are therefore not to beconsidered limiting of its scope, for the invention may admit to otherequally effective embodiments.

FIG. 1 is a GPC chromatogram of polyurethanes obtained in accordancewith one or more embodiments of the invention.

DETAILED DESCRIPTION

In accordance with various embodiments of the invention, provided arenovel thickeners for water-comprising preparations, in particularcosmetic preparation. The novel thickeners should have the bestthickening effect possible. Moreover, the thickening effect of the novelthickeners should at least not be diminished by the presence of salts inthe aqueous preparations.

According to other embodiments of the invention, the polyurethanethickeners are tin-free, since this is desired for cosmeticapplications.

Accordingly, one aspect of the invention relates to a process forpreparing polyurethanes comprising

I) at least two hydrophilic sections S,II) at least one hydrophilic section P different from S,III) at least two terminal hydrophobic sections T,IV) at least two hydrophobic sections D different from T, wherea) to each section T is directly attached a section S,b) to each section S on at least one side is attached at least onesection D,c) to each section P are attached at least two sections D,wherein the preparation takes place in the presence of at least onecarboxylic acid salt of a metal selected from the group consisting ofalkali metals, alkaline earth metals and mixtures thereof.

The polyurethanes obtainable by the process according to one or moreembodiments of the invention are mixtures which comprise at least someof the described polyurethane structures. The polyurethanes obtainableby the process according to one or more embodiments of the inventionare, in some embodiments, dispersible in water. According to theinvention, this comprises that they can also be emulsified in water orare completely or partially soluble in water.

The polyurethanes obtainable by the process according to one or moreembodiments of the invention (also referred to herein below as“polyurethanes according to the invention”) may be at least partiallybranched. “At least partially branched” means that at least some of thepolymer molecules are not linear, but have branching points.

Such branches may be present both in the hydrophobic sections and alsothe hydrophilic sections.

In one embodiment of the invention, at least some of the terminalhydrophobic sections T are branched.

In one embodiment of the invention, at least some of the hydrophobicsections D are branched.

One advantage of the polyurethanes obtainable according to variousembodiments of the invention is that by using alkali(ne earth) metalcarboxylates, it is possible to generate branches of the polyisocyanatesin the form of isocyanurate or allophanate structures in-situ and it istherefore not necessary to rely on polyisocyanates with already preparedisocyanurate or allophanate structures as starting compounds. Firstly,the starting materials are more favorable in terms of cost as a resultand secondly the desired amount of such branching points can be adjustedto the desired degree via the amount of catalyst. Furthermore, theprocess according to one or more embodiments of the invention leads lessquickly to crosslinked structures than the use of prepared isocyanurateor allophanate structures.

The backbone of the polyurethanes according to various embodiments ofthe invention is composed of alternating hydrophobic and hydrophilicsections, where the hydrophobic and hydrophilic sections alternate inthe sequence, but may be different in terms of their size, length andnature. In the polyurethanes according to the invention, a hydrophobicsection is, in some embodiments, attached on both sides to a hydrophilicsection. These hydrophobic sections may independently of one another beidentical or different. Each section may be short-chain or an oligomerradical or a polymer radical. In the present case, “attached to asection” is understood as meaning that the connection takes placedirectly, i.e. that the two sections in question are directly adjacentin the polymer molecule.

Hydrophilic Sections

Hydrophilic is the term used here to refer to those sections whichexhibit marked interaction with water. In general, hydrophilic sectionsconsist of radicals of substances which are themselves hydrophilic.

Typical hydrophilic groups known to the person skilled in the art are,for example, nonionic polyether radicals. Polyether radicals may behomo-alkylene oxide radicals or mixtures of different alkylene oxideradicals. These different alkylene oxide radicals may be present in thepolyether radicals in random distribution or be present in block form.Specific polyether radicals are homo-ethylene oxide radicals. Hereinbelow, ethylene oxide is also referred to as EO, and propylene oxide isalso referred to as PO.

According to another embodiment, the polyether radicals comprisemixtures of EO radicals and PO radicals. These may be present in thepolyether radicals in random distribution or be present in block form.In one specific embodiment, the EO and PO radicals are present in blockform.

A more specific embodiment includes polyether radicals which have atleast 50% by weight of ethylene oxide radicals, for example polyetherradicals which have more than 50% by weight of ethylene oxide radicals,and propylene oxide radicals as further alkylene oxide radicals. In veryspecific embodiments, the polyether radicals consist of ethylene oxideradicals.

The hydrophilicity of a substance can be determined, for example, bymeans of an opacity measurement of an aqueous solution.

Specific hydrophilic sections are water-soluble. For the purposes ofthis invention, a substance is referred to as being soluble in a liquidphase if at least 1 g, and in some embodiments at least 10 g, of thesubstance dissolved at 20° C. and a pressure of 1 bar to give a solutionthat looks clear to the human eye, i.e. without visible clouding in 1liter of the liquid phase. Water-soluble substances are thereforesubstances which are soluble in an amount of at least 1 g, and in someembodiments at least 10 g, at 20° C. and a pressure of 1 bar to give asolution that looks clear to the human eye, i.e. without visibleclouding, in 1 liter of water, and in some embodiments demineralizedwater.

Hydrophobic Sections

By means of the process according to one or more embodiments of theinvention, polyurethane molecules are obtained which comprise at leasttwo terminal hydrophobic sections T and at least two hydrophobicsections D.

However, depending on how the reaction is carried out, polyurethanemolecules are also obtained which comprise two hydrophobic sections Tand only one hydrophobic section D.

In general, the hydrophobic sections consist of radicals of substanceswhich are immiscible with water or only poorly miscible with water andare, in some embodiments, lipophilic at the same time, i.e. are readilysoluble in nonpolar solvents such as, for example, fats and oils.

Typical hydrophobic sections T are, for example, hydrocarbon radicals,in particular long-chain hydrocarbon radicals.

In one embodiment of the invention, the hydrocarbon radicals areunbranched. In another embodiment of the invention, the hydrocarbonradicals are branched.

In a further embodiment of the invention, the polyurethanes according tothe invention comprise both branched and unbranched hydrocarbonradicals.

Long-chain aliphatic alcohols, aromatic alcohols and aliphaticdiisocyanates are examples of hydrophobic substances, the radicals ofwhich may be present in the hydrophobic sections of the polyurethanesaccording to the invention.

The polyurethanes prepared by the process according to one or moreembodiments of the invention comprise at least two terminal hydrophobicsections (T) which, independently of one another, may be identical ordifferent.

In one specific embodiment, at least some of the polyurethanes accordingto the invention comprise more than two terminal hydrophobic sections(T).

The terminal hydrophobic sections T can be branched or unbranched. Inspecific embodiments, at least one of the two terminal hydrophobicsections T is branched.

According to some embodiments, the terminal hydrophobic sections Tcomprise at least one alkyl radical. In specific embodiments, this alkylradical comprises 4 to 30 carbon atoms, particularly 8 to 30 and in veryspecific embodiments 12 to 30 carbon atoms.

In certain embodiments, the chain length of the main chain of the alkylradicals which are present in the sections T is in the range from 4 to30 carbon atoms. These are for example alkyl radicals of linear orbranched alkanes such as, for example, butane, isobutane, pentane,isopentane, neopentane, hexane, heptane, octane, 2-ethylhexane, nonane,decane, undecane, dodecane, tridecane, isotridecane, tetradecane,pentadecane, hexadecane, heptadecane, octadecane, nonadecane, icosane,henicosane, docosane, tricosane, isotricosane, tetracosane, pentacosane,hexacosane, heptacosane, octacosane, nonacosane, triacontane,2-octyldodecane, 2-dodecylhexadecane, 2-tetradecyloctadecane, ormonomethyl-branched isooctadecane.

The hydrophobic sections T can likewise also comprise radicals ofcycloalkanes and -alkenes, as described for example in EP 761780 A2, p.4, ll. 56-58, radicals of alkenes as described for example in EP 761780A2, p. 4, ll. 51-52, or alkylaryl radicals as described for example inEP 761780 A2, p. 4, ll. 53-55.

According to some embodiments, the sections T particularly comprise theabove-described alkyl radicals with 8 to 30 carbon atoms, and inspecific embodiments, with 12 to 30 carbon atoms.

The sections T may either consist of or comprise the above-describedaliphatic radicals, but may also comprise the above-described aromaticradicals or consist of them.

In one specific embodiment, at least one section T is a branched alkylradical.

In another embodiment, the side chains of the branched alkyl radicalshave a chain length of at most 6, and in a specific embodiment, at most4 carbon atoms.

In one embodiment, the branches are considerably shorter than the mainchain. In one embodiment, each branch of the sections T of thepolyurethanes according to the invention has a chain length whichcorresponds at most to half of the chain length of the main chain ofthis section T. In one specific embodiment, the branched alkyl radicalsare iso- and/or neo-alkyl radicals. In one specific embodiment, radicalsof isoalkanes are used as branched alkyl radicals. In a particularembodiment, the radical comprises a C₁₃-alkyl radical, and in an evenmore particular embodiment, an iso-C₁₃-alkyl radical.

In another embodiment, the sections T comprise branched alkyl radicals,the side chains of which have a chain length of at least 4, and in aspecific embodiment, of at least 6, carbon atoms.

The sections T can be introduced into the polyurethanes according to theinvention in various ways.

In one specific embodiment, the sections T are introduced into thepolyurethanes simultaneously and together with the hydrophilic sectionsS through the use of alkoxylated alcohols.

Suitable alcohols are, for example, the alkoxylated

-   -   linear alcohols from natural sources or from the Ziegler        build-up reaction of ethylene in the presence of aluminum alkyl        catalysts. Examples of suitable alcohols are C₆-C₃₀-alcohols, in        particular C₁₂-C₃₀-alcohols. Particularly specific alcohols        which may be mentioned here are: n-dodecanol, n-tetradecanol,        n-hexadecanol, n-octadecanol, n-eicosanol, n-docosanol,        n-tetracosanol, n-hexacosanol, n-octacosanol and/or        n-triacontanol, and also mixtures of the aforementioned        alcohols, for example NAFOL® grades such as NAFOL® 22+ (Sasol).    -   oxo alcohols such as, for example, isoheptanol, isooctanol,        isononanol, isodecanol, isoundecanol, isotridecanol (for example        Exxal® grades 7, 8, 9, 10, 11, 13).    -   alcohols which are branched in the 2 position; these are the        Guerbet alcohols known to the person skilled in the art which        are accessible by dimerization of primary alcohols via the        so-called Guerbet reaction. Particularly specific embodiments of        alcohols which may be mentioned here are: Isofol®12 (Sasol),        Rilanit®G16 (Cognis).    -   alcohols which are obtained by the Friedel-Crafts alkylation        with oligomerized olefins and which then comprise an aromatic        ring as well as a saturated hydrocarbon radical. Particularly        specific embodiments of alcohols which may be mentioned here        are: isooctylphenol and isononylphenol.    -   alcohols of the general formula (4) in EP 761780 A2, p. 4

or alcohols of the general formula (5) in EP 761780 A2, p. 4

where

-   -   R⁴, R⁵, R⁷ and R⁸, independently of one another, have the        meaning described in EP 761780 A2, p. 4, lines 45 to 58; more        specifically, R⁴, R⁵, R⁷ and R⁸, independently of one another,        are alkyl radicals having at least 4 carbon atoms and the total        number of the carbon atoms in the alcohols is at most 30,    -   R⁶ is an alkylene radical such as, for example, —CH₂—,        —CH₂—CH₂—, —CH₂—CH(CH₃)—.

By way of example, mention may be made here of 2-decyl-1-tetradecanol assuitable alcohol.

In one embodiment, mixtures of ethoxylated C₁₆-C₁₈-fatty alcohols areused in order to introduce sections T into the polyurethanes.

In a further embodiment, ethoxylated iso-C₁₃-oxo alcohols or mixturesthereof are used in order to introduce sections T into thepolyurethanes.

In a further embodiment, mixtures comprising ethoxylated C₁₆-C₁₈-fattyalcohols and ethoxylated iso-C₁₃-oxo alcohols are used in order tointroduce sections T into the polyurethanes.

In a further embodiment, the above-described alcohols of the generalformula (4) or (5) in EP 761780 A2, p. 4, are used in their ethoxylatedform in order to introduce sections T into the polyurethanes.

It is of course possible to additionally also introduce other sections Tinto the polyurethanes.

The hydrophobic sections T can of course also be introduced into thepolyurethanes through any desired mixtures of the above-describedethoxylated alcohols.

By means of the process according to one or more embodiments of theinvention, as is customary in the case of polymerization reactions,mixtures of different polymers are of course obtained, in the presentcase thus mixtures of different polyurethanes.

The term “polyurethane” used here can refer either to any individualpolyurethane molecule or to the totality of the polyurethane moleculesobtainable by the process according to one or more embodiments of theinvention.

The polyurethanes obtainable by the preparation process according to oneor more embodiments of the invention are, in some embodiments, mixtureswhich comprise the described polyurethane structures.

Accordingly, the preparation of mixtures of polyurethanes, the terminalhydrophobic sections T of which are branched and/or unbranched alkylradicals is also in accordance with the invention. The preparation ofmixtures which comprise polyurethanes which comprise both branched andunbranched terminal, hydrophobic sections T is also in accordance withthe invention.

In some specific embodiments, at least some of the polyurethanemolecules obtainable by the process according to one or more embodimentsof the invention comprise allophanate segments. The invention thus alsoprovides a process according to one or more embodiments of the inventionwhere at least some of the resulting polyurethanes comprise allophanatesegments.

In some specific embodiments, at least some of the polyurethanemolecules obtainable by the process according to one or more embodimentsof the invention comprise isocyanurate segments.

The invention thus also provides a process according to one or moreembodiments of the invention where at least some of the polyurethanescomprise isocyanurate segments.

Hydrophilic Sections S

In the polyurethanes obtainable by the process according to one or moreembodiments of the invention, to the terminal hydrophobic sections T areattached hydrophilic sections S.

In the polyurethanes, the sections S, independently of one another, maybe identical or different, linear or branched.

In one embodiment, the hydrophilic sections S are of different lengthsand linear.

In specific embodiments, the sections S may comprise radicals ofalkylene oxides. In further embodiments, the number is in the range from2 to 150 alkylene oxide radicals, or more specifically, in the rangefrom 5 to 100 alkylene oxide radicals and in very specific embodimentsin the range from 10 to 100 alkylene oxide radicals.

In another specific embodiment, the hydrophilic sections S may compriseor consist of ethylene oxide radicals. In one specific embodiment, thehydrophilic sections S comprise ethylene oxide radicals (EO units), thenumber of which is in the range from 2 to 150 EO units, in specificembodiments in the range from 5 to 100 EO units and in very specificembodiments in the range from 10 to 100 EO units.

In one specific embodiment, the sections S consist of 5 to 30, and insome embodiments, 10 to 25 EO units.

In another embodiment, the sections S consist of 30 to 100, and in someembodiments, 40 to 100 EO units.

The number of EO units per molecule of ethoxylated alcohol is alsoreferred to as degree of ethoxylation.

The ethoxylated alcohols used in the process according to one or moreembodiments of the invention have a degree of ethoxylation which is inthe range from 2 to 150 ethylene oxide radicals, and in someembodiments, in the range from 5 to 100 ethylene oxide radicals and, inspecific embodiments, in the range from 10 to 100 ethylene oxideradicals.

In a particularly specific embodiment, the ethoxylated alcohols usedhave a degree of ethoxylation in the range from 10 to 25 ethylene oxideradicals.

In one embodiment, a branched, nonionic compound of the structuralformula RO(CH₂CH₂O)_(x)H, where R is a C₁₃-alkyl radical, and in someembodiments, an iso-C₁₃-alkyl radical, and where x=3, 5, 6, 6.5, 7, 8,10, 12, 15 or 20, and in some embodiments, x=10, is used as at least oneof the alcohols used. Commercially, such an ethoxylated, alkyl-branchedalcohol is available, for example, as Lutensol®TO10.

In one embodiment, at least one of the alcohols used is an alcohol ofthe general formula (4) in EP 761780 A2, p. 4

or an alcohol of the general formula (5) in EP 761780 A2, p. 4

where

-   -   R⁴, R⁵, R⁷ and R⁸, independently of one another, have the        meaning described in EP 761780 A2, p. 4, lines 45 to 58; in some        embodiments, R⁴, R⁵, R⁷ and R⁸, independently of one another,        are alkyl radicals having at least 4 carbon atoms and the total        number of the carbon atoms in the alcohols is at most 30,    -   R⁶ is an alkylene radical, such as, for example, —CH₂—,        —CH₂—CH₂—, —CH₂—CH(CH₃)—.

By way of example, mention may be made here of 2-decyl-1-tetradecanol asa suitable alcohol.

In one embodiment of the invention, mixtures of ethoxylated linear andethoxylated branched long-chain alcohols, in particular mixtures of theaforementioned types, are used.

In one embodiment of the invention, the hydrophilic sections S comprisemixtures of EO and PO units.

The sections S can likewise comprise longer-chain alkylene oxideradicals, with the proviso that the sections S must be hydrophilicoverall. The hydrophilicity can be controlled for example via thefraction of EO units in the sections S.

Hydrophobic Sections D

To each hydrophilic section S is attached at least one hydrophobicsection D. Here, a section S may also be present in the interior of themolecule of the polyurethanes according to the invention. In this case,this section S is connected not like an edge-position section S to asection D and a section T, but on at least two sides to sections D. Incertain specific embodiments, a section S is connected in the interiorof the molecule on both sides to one section D in each case.

For all edge-position sections S, it is the case that they are directlyconnected to an end-position section T. Should a section S be branchedto a low extent, then it could be directly connected at two or morepositions to hydrophobic sections D. In certain specific embodiments, toeach hydrophilic section S is connected a hydrophobic section D on atleast one side.

In a particularly specific embodiment, all sections S are unbranched andedge-positioned and connected to a section T on one side and to asection D on the other side.

By means of the process according to one or more embodiments of theinvention, polyurethane molecules are obtained which comprise at leasttwo hydrophobic sections D. In addition, however, depending on how theprocess according to one or more embodiments of the invention is carriedout, polyurethane molecules are also obtained which comprise only onehydrophobic section D.

In the polyurethane molecules with at least two hydrophobic sections D,these may be identical or, independently of one another, different.

The sections D can be branched with short-chain hydrophobic branches orbe unbranched. In certain specific embodiments, at least some of thesections D are branched.

In certain specific embodiments, the sections D comprise at least onehydrophobic chain of carbon atoms, the length of which is in the rangefrom 2 to 20 carbon atoms, and in some embodiments, 3 to 16 carbon atomsand in particular in the range from 4 to 12 carbon atoms.

In certain specific embodiments, the sections D comprise diisocyanateradicals. The sections D, in specific embodiments, comprise radicals ofaliphatic diisocyanates. Thus, for example, a hydrophobic section D canconsist of one or more aliphatic diisocyanate radicals. In certainspecific embodiments, a section D consists of one to ten aliphaticdiisocyanate radicals, in specific embodiments, of one to five aliphaticdiisocyanate radicals; in very specific embodiments, it comprises one,two or three aliphatic diisocyanate radicals.

The hydrophobic sections D can comprise aliphatic diisocyanate radicalswith long, mid-length or short aliphatic units.

In one of the specific embodiments, the sections D of the polyurethanesprepared by the process according to one or more embodiments of theinvention are cycloaliphatic or aliphatic diisocyanate radicals.

Aliphatic diisocyanate radicals are particularly specific embodiments ofas sections D. Aliphatic diisocyanates which may be mentioned by way ofexample are: 1,4-butylene diisocyanate, 1,12-dodecamethylenediisocyanate, 1,10-decamethylene diisocyanate,2-butyl-2-ethylpentamethylene diisocyanate, 2,4,4- or2,2,4-trimethylhexamethylene diisocyanate and in particularhexamethylene diisocyanate (HDI).

By way of example, cycloaliphatic diisocyanates which may be mentionedare: isophorone diisocyanate (IPDI), 2-isocyanatopropylcyclohexylisocyanate, 4-methylcyclohexane 1,3-diisocyanate (H-TDI) and1,3-bis(isocyanatomethyl)cyclohexane.

So-called H₁₂-MDI or diisocyanates termed “saturated MDI”, such as, forexample, 4,4′-methylenebis(cyclohexyl isocyanate) (alternatively alsocalled dicyclohexylmethane 4,4′-diisocyanate) or2,4′-methylenebis(cyclohexyl) diisocyanate can also be present asradicals in sections D of the polyurethanes PU according to theinvention.

It is of course possible, in the process according to one or moreembodiments of the invention, to use mixtures of the abovementioneddiisocyanates in order to prepare mixtures of different polyurethanes.

In one specific embodiment, some of the polyurethanes obtainable by theprocess according to one or more embodiments of the invention comprisehydrophobic sections D with allophanate structures. Allophanatestructures are formed as a result of the addition of an isocyanate grouponto a urethane unit.

In one specific embodiment, some of the polyurethanes prepared by theprocess according to one or more embodiments of the invention comprisehydrophobic sections D with isocyanurate structures. Isocyanuratestructures are formed by the addition of 3 isocyanate groups(trimerization).

In a further specific embodiment, some of the polyurethanes prepared bythe process according to one or more embodiments of the inventioncomprise both hydrophobic sections D with allophanate structures andalso hydrophobic sections D with isocyanurate structures.

In a further embodiment, some of the polyurethanes prepared by theprocess according to one or more embodiments of the invention comprisehydrophobic sections D with biuret structures. Biuret structures areformed as a result of the addition of an isocyanate group onto a ureaunit. Urea units in turn are formed as a result of the addition ofprimary amines onto isocyanate groups.

Hydrophilic Sections P

As a result of the process according to one or more embodiments of theinvention, polyurethane molecules are obtained which comprise at leastone hydrophilic section P different from the hydrophilic sections S. Inthis case, to P are attached at least two hydrophobic sections D. Thesections P of the polyurethanes according to the invention can,independently of one another, be identical or different.

Depending on how the process according to one or more embodiments of theinvention is carried out, however, polyurethane molecules are alsoadditionally obtained which comprise no hydrophilic section P.

If more than one section P is present in a polyurethane according to theinvention, then there is in each case at least one hydrophobic section Dbetween the hydrophilic sections P. If more than one section P ispresent in a polyurethane according to the invention, then these may beidentical or different.

In one embodiment, the polyurethanes according to the invention cancomprise a sequence of sections in the order hydrophobic section D, thenhydrophilic section S, then hydrophobic section D again between twohydrophilic sections P. Thus, if in a polyurethane according to theinvention, more than one section P is present, then in such a case, thesections in the interior of the molecule can have a sequence of P-D-P orof P-D-S-D-P. Should more than two sections P be present, then bothsequences in one molecule are possible.

In certain specific embodiments, only one or two sections P are presentin a molecule of the polyurethanes obtainable according to theinvention.

The hydrophilic sections P are, in specific embodiments, introduced intothe polyurethanes through the use of hydrophilic polyols. Per molecule,these comprise at least two OH groups and at least two functional groupswhich are selected from the functions —O— (ether groups) and —COO—(ester groups), where the molecular weight of these hydrophiliccompounds is at least 300 and, in specific embodiments, at least 1200.

One embodiment of the invention is a process according to one or moreembodiments of the invention, wherein the at least one hydrophilicsection P has a number-average molecular weight of from 1500 to 20 000g/mol, and in some embodiments, from 4000 to 12 000 g/mol.

Suitable hydrophilic polyols are, for example, the polymerizationproducts of ethylene oxide, the copolymerization or graft polymerizationproducts thereof, and the polyethers obtained by condensation ofpolyhydric alcohols or mixture thereof and the polyethers obtained byethoxylation of polyhydric alcohols, amides, polyamides and aminoalcohols. Examples thereof are, for example, polyethylene glycols,addition products of ethylene oxide onto trimethylolpropane, EO-PO blockcopolymers, OH-terminated polyesters, such as, for example, those of themultifunctional polycaprolactone type.

Specific embodiments of hydrophilic polyols are polyetherpolyols. Theseare those hydrophilic polyols which comprise at least two OH groups andat least two —O— functions (ether groups) per molecule. Thesepolyetherpolyols are generally so hydrophilic that they arewater-soluble at room temperature (20° C.).

Of suitability for preparing the polyurethanes by the process accordingto one or more embodiments of the invention are those polyetherpolyolswhich comprise predominantly polyethylene glycol. In very specificembodiments, these polyethylene glycols have an average amount of EOunits in the range from 30 to 450 per molecule.

In specific embodiments, polyols of the general formulaHO—(CH₂—CH₂—O)_(n)—H, where n can assume the values 30 to 450 are used.These are polyethylene glycols, which are condensation products ofethylene oxide with ethylene glycol or water.

In certain specific embodiments, the molecular weight of thesepolyethylene glycols is adjusted to values in the range from 1500 to 20000 g/mol.

However, it is also possible to use EO-PO block copolymers in order toincorporate the sections P into the polyurethanes obtainable accordingto the invention. For example, it is possible to use EO-PO blockcopolymers of the general formula HO-(EO)_(m)-(PO)_(n)-(EO)_(O)—H, wherem and o, independently of one another, are integers in the range from 10to 100, and in some embodiments, from 20 to 80, n is an integer in therange from 5 to 50, and in some embodiments, from 20 to 40, and where m,n and o are selected such that HO-(EO)_(m)-(PO)_(n)-(EO)_(O)—H iswater-soluble.

According to the invention, the essentially linear polyether radicalswhich form the sections P, in specific embodiments, have anumber-average molecular weight M_(n) of at least 1500 g/mol and at most20 000 g/mol.

In a specific embodiment, the essentially linear polyether radicals havenumber-average molecular weights in the range from 1500 g/mol to 15 000g/mol.

In a further specific embodiment, the essentially linear polyetherradicals have number-average molecular weights in the range from 4000g/mol to 12 000 g/mol.

In a particularly specific embodiment, the essentially linear polyetherradicals have number-average molecular weights in the range from 6000g/mol to 10 000 g/mol.

In a particularly specific embodiment, the linear polyether radicalshave a number-average molecular weight M_(n) of about 10 000 g/mol.

In a further particularly specific embodiment, the linear polyetherradicals have a number-average molecular weight M_(n) of about 6000g/mol.

All of the hydrophilic sections of the polyurethanes obtainable by theprocess according to one or more embodiments of the invention, i.e. thesections S and P, may be polyether radicals.

In one specific embodiment, the hydrophilic sections of thepolyurethanes according to the invention consist of

-   -   polyalkylene oxide units (sections P) and    -   polyethylene oxide units (sections S).

In one particularly specific embodiment of the polyurethanes obtainableby the process according to one or more embodiments of the invention,all of the sections P and S consist of EO units.

As a result of the process according to one or more embodiments of theinvention, polyurethane molecules are obtained which comprise at leastthree hydrophilic sections. In one of the specific embodiments, theseare two sections S and at least one section P.

Additionally, however, depending on the reaction procedure, polyurethanemolecules with only two hydrophilic sections S and without hydrophilicsection P are also obtained.

As a result of the process according to one or more embodiments of theinvention, polyurethanes are therefore also obtained, according to theinvention, which comprise

I) at least two hydrophilic sections S,II) no hydrophilic section P,III) at least two terminal hydrophobic sections T,IV) at least one hydrophobic section D different from T,wherea) to each section T is directly attached a section S,b) to each section S is attached a section D.

The polyurethanes prepared by means of the process according to one ormore embodiments of the invention which additionally compriseallophanate structures comprising at least three sections S and at leastone section P.

Depending on the reaction procedure, however, polyurethanes are alsoadditionally obtained which comprise allophanate structures and at leastthree sections S, but no section P.

Polyurethanes prepared by the process according to one or moreembodiments of the invention which additionally comprise isocyanuratestructures may, in specific embodiments, comprise at least threesections S and at least one section P.

Depending on the reaction procedure, however, polyurethanes are alsoadditionally obtained which comprise isocyanurate structures and atleast three sections S, but no section P.

At least some of the polyurethanes prepared by the process according toone or more embodiments of the invention are linear and have thefollowing sequence of sections: T-S-D-P-D-S-T or T-S-D-P-D-P-D-S-T.Depending on the reaction procedure, however, polyurethanes are alsoadditionally obtained which have the sequence T-S-D-S-T.

In one specific embodiment of the invention, at least some of thepolyurethanes prepared by the process according to one or moreembodiments of the invention comprise allophanate and/or isocyanuratestructures and have the following sequence of sections:

For example, polyurethanes prepared by the process according to one ormore embodiments of the invention which additionally compriseallophanate structures have the following structure:

For example, polyurethanes prepared by the process according to one ormore embodiments of the invention which additionally compriseisocyanurate structures have the following structure:

For each section P, it is the case that its molecular weight is greaterthan that of each section S present in the same molecule.

The ratio of the molecular weights M_(n) of each hydrophilic section Sof the polyurethanes according to the invention to the molecular weightof each hydrophilic section P is in the range from 1:1.4 to 1:140, andin some embodiments, in the range from 1:1.7 to 1:120.

In one specific embodiment, the ratio is 1:x, where x is equal to orgreater than 2, and in some embodiments, equal to or greater than 2.3and in a more specific embodiment, x is equal to or greater than 2.8.The ratio may be, in specific embodiments, in the range from 1:2.8 to1:115, in very specific embodiments in the range from 1:3 to 1:95 and,in even more specific embodiments, in the range from 1:3.4 to 1:80.

As a result of the process according to one or more embodiments of theinvention, mixtures of different polyurethanes are generally obtained.Such a mixture can comprise e.g. polyurethanes which have the samesequence of the sections T, S, D and/or P, but differ from one anotherstructurally in at least one of the sections. One example of this whichmay be mentioned is a different section structure or a different sectionchain length. Thus, the sections T in a mixture of the polyurethanesprepared by the process according to one or more embodiments of theinvention can be different. For example, a mixture according to theinvention can comprise polyurethanes, the sections T of which are allbranched, and/or those, the sections T of which are all linear, and/orthose polyurethanes which comprise both at least one linear section Tand also at least one branched section T.

In one embodiment, the sum of the molecular weights of all sections Tplus the molecular weights of sections D should be kept less than orequal to the sum of the molecular weights of all of the sections P.

Catalyst

To prepare the polyurethanes by the process according to one or moreembodiments of the invention, the catalyst used is carboxylic acid saltsof alkali metals, carboxylic acid salts of alkaline earth metals ormixtures thereof.

The carboxylic acids, the alkali(ne earth) metal salts of which are usedas catalysts in the process according to one or more embodiments of theinvention, are, in specific embodiments, monocarboxylic acids of thegeneral formula R—COOH, where R can be any desired organic, for examplean aliphatic, an aromatic or a heterocyclic radical.

In certain specific embodiments, R is an aliphatic radical, thus forexample an alkyl radical, an alkenyl radical or an alkynyl radical. Rcan also comprise heteroatoms; for example, the carboxylic acid may be ahydroxycarboxylic acid.

In one embodiment of the invention, R is a hydrocarbon radical having 1to 20, and in some embodiments, having 1 to 12, carbon atoms. R may belinear or branched, saturated or unsaturated.

In one embodiment of the invention, the carboxylic acid is acetic acid.

In a further embodiment of the invention, the carboxylic acid isoctanoic acid.

In a further embodiment of the invention, the carboxylic acid is2-ethylhexanoic acid.

In a further embodiment of the invention, the carboxylic acid isneodecanoic acid.

In a further embodiment of the invention, the carboxylic acid isn-decanoic acid.

In a further embodiment of the invention, the carboxylic acid is stearicacid.

In a further embodiment of the invention, the carboxylic acid isricinoleic acid ((9Z,12R)-12-hydroxy-9-octadecenoic acid).

In a further embodiment of the invention, the carboxylic acid is ahydroxycarboxylic acid, such as, for example, citric acid or lacticacid, in particular lactic acid.

If at least one carboxylic acid salt of an alkali metal is selected ascatalyst, then the alkali metal is, in specific embodiments, selectedfrom sodium and potassium, particularly, and in even more specificembodiments, potassium.

If at least one carboxylic acid salt of an alkaline earth metal isselected as catalyst, then the alkaline earth metal is, in specificembodiments, selected from calcium and magnesium, in even more specificembodiments, calcium.

In one specific embodiment of the invention, the catalyst used for thepreparation of the polyurethanes by the process according to one or moreembodiments of the invention is potassium acetate.

In one specific embodiment of the invention, the catalyst used for thepreparation of the polyurethanes by the process according to one or moreembodiments of the invention is potassium lactate.

It is of course also possible to use mixtures of two or more carboxylicacid salts of alkali(ne earth) metals as catalysts for preparingpolyurethanes PU according to the invention.

In one specific embodiment, one catalyst is used.

In addition to these catalysts, further catalysts known to the personskilled in the art in the field of polyurethane preparation can be used.

Such catalysts usually used in polyurethane chemistry are organicamines, in particular tertiary aliphatic, cycloaliphatic or aromaticamines, and Lewis-acidic organic metal compounds.

Suitable Lewis-acidic organic metal compounds are e.g. metal complexessuch as acetylacetonates of iron, titanium, zinc, aluminum, cobalt,manganese, nickel and zirconium, such as e.g. zirconium2,2,6,6-tetramethyl-3,5-heptanedionate. Further suitable metal compoundsare described by Blank et al. in Progress in Organic Coatings, 1999, 35,19 ff.

Bismuth, cobalt or zinc catalysts and also cesium or titanium salts canalso be used as catalysts.

In one embodiment of the invention, the amount of such further catalystswhich are not carboxylic acid salts of alkali metals, carboxylic acidsalts of alkaline earth metals or mixtures thereof, is at most 10% byweight, and in some embodiments, at most 5% by weight, and in morespecific embodiments, at most 1% by weight and in particular at most0.1% by weight, of the total amount of catalyst.

One embodiment of the invention is the process according to one or moreembodiments of the invention wherein the preparation takes place in thepresence of less than 10 ppm of tin.

A further embodiment of the invention is the process according to one ormore embodiments of the invention wherein the preparation takes place inthe presence of less than 10 ppm of zinc.

In a further embodiment of the invention, apart from the at least onecarboxylic acid salt of at least one metal selected from alkali metals,alkaline earth metals and mixtures thereof, no further catalysts areused for preparing the polyurethanes.

The catalyst or the mixture of catalysts is, in specific embodiments,used in an amount in the range from 50 ppm to 5000 ppm, based on thetotal weight of all reacting compounds. In certain specific embodiments,the catalyst is used in an amount in the range from 50 to 2500 ppm, andin more specific embodiments, in an amount in the range from 100 to 1000ppm, based on the total weight of all reacting compounds.

The catalyst can be added to the reaction mixture in solid or liquidform, depending on the nature of the catalyst. Suitable solvents arenon-aqueous solvents such as, for example, aromatic or aliphatichydrocarbons, inter alia toluene, xylene, ethyl acetate, hexane andcyclohexane, and also carboxylic acid esters, such as, for example,ethyl acetate. Furthermore suitable solvents are acetone, THF, DMSO,DMF, DMAc and N-methylpyrrolidone and M-ethylpyrrolidone.

The catalyst/catalyst mixture is, in specific embodiments, used indissolved form, and in even more specific embodiments, dissolved in thepolyetherpolyols with which the hydrophilic sections P are introducedinto the polyurethanes.

The catalyst may already be present, at least partially, in thepolyetherpolyols used for the process according to one or moreembodiments of the invention if, during the preparation thereof,carboxylic acid salts of alkali(ne earth) metals have been used or havebeen formed.

In one embodiment of the invention, the polyetherdiols used in theprocess according to one or more embodiments of the invention thuscomprise at least some of the catalyst, if appropriate the totalrequired amount of catalyst.

In one embodiment of the invention, the polyetherdiols used in theprocess according to one or more embodiments of the invention prior tothe start of the process already comprise at least some of the requiredcatalyst and the remainder is added to carry out the process.

In the process according to one or more embodiments of the invention forpreparing the polyurethanes, and in particular embodiments, thefollowing starting materials are used:

-   -   A) Compounds which introduce the hydrophilic sections P into the        polyurethanes: in specific embodiments, polyols of the general        formula HO—(CH₂—CH₂—O)_(n)—H, where n, in specific embodiments,        assumes the values 30 to 450; these are polyethylene glycols        which are condensation products of ethylene oxide with ethylene        glycol or water. Specific embodiments of polyethylene glycols        have a number-average molecular weight in the range from 6000 to        12 000 g/mol and particularly specific embodiments of ones have        a number-average molecular weight of from 6000 to 10 000 g/mol.    -   B) Compounds which introduce the terminal hydrophobic sections T        and the hydrophilic sections S adjacent in each case to the        sections T: in specific embodiments, ethoxylated C₁₆-C₁₈-fatty        alcohols, ethoxylated iso-C₁₃-oxo alcohols, ethoxylated branched        alcohols as in Production Examples 1 to 24 of EP 761780 A2 and        mixtures thereof.    -   C) Compounds which introduce the hydrophobic sections D:        aliphatic diisocyanates, in particular hexamethylene        diisocyanate (HDI).

The process according to one or more embodiments of the invention forthe preparation of the polyurethanes comprises, in one embodiment, thefollowing steps:

-   -   I) preparation of a mixture comprising        -   a. at least one polyetherdiol with a molecular weight in the            range from 6000 to 12 000 g/mol,        -   b. at least one alkyl-branched C₈-C₃₀-, and in some            embodiments, C₁₂-C₃₀-alkanol which has been ethoxylated with            10 to 100 mol, and in specific embodiments, with 10 to 40            mol, and in more specific embodiments, with 10 to 25 mol, of            ethylene oxide per mol of alkanol,        -   c. at least one carboxylic acid salt of at least one alkali            metal or alkaline earth metal, and in some embodiments, a            potassium carboxylate,    -   II) optionally heating the mixture from step I) to 60 to 120°        C., and in some embodiments, to 80 to 100° C.;    -   III) if appropriate, reducing the water content of the mixture        to a water content of at most 1000 ppm, and in some embodiments,        at most 300 ppm, based in each case on the total weight of the        mixture;    -   IV) addition of at least one diisocyanate, and in some        embodiments, hexamethylene diisocyanate, to the mixture;    -   V) leaving the resulting reaction mixture to react until the        isocyanate content is at most 0.1% by weight, based on the total        weight of the reaction mixture.

Reaction mixture is understood as meaning the totality of all substanceswhich are present in the reaction space after the point at which thetotal amount of catalysts, isocyanates, substances reactive towardsisocyanates and all further substances, such as for example solvents,have been completely supplied to the reaction space.

Solvents is understood as meaning phases that are liquid at 20° C. and apressure of 1 bar in which one or more of the starting materials for thepolyurethanes, i.e. the substances which introduce the hydrophilicand/or hydrophobic sections into the polyurethanes or which act ascatalyst, are soluble at 20° C. and 1 bar.

In one embodiment of the invention the amount of solvents which aredifferent from the substances which introduce the hydrophilic andhydrophobic sections into the polyurethanes or which act as catalyst isin the range from 0 to 10% by weight, and in more specific embodiments,from 0 to 5% by weight and in particular 0 to 1% by weight, based ineach case on the weight of the reaction mixture.

In one embodiment of the invention, the process according to one or moreembodiments of the invention is carried out essentially in the absenceof solvents which are different from the substances which introduce thehydrophilic and/or hydrophobic sections into the polyurethanes or whichact as catalyst.

In one embodiment of the invention, the amount of such substances which,following the complete addition of all substances during the reaction,are present in the reaction space and are neither catalysts, norsubstances which are incorporated into the polyurethanes which form andconsequently introduce the hydrophilic and hydrophobic sections into thepolyurethanes, nor reaction products, is at most 10% by weight, and insome embodiments, at most 5% by weight, an in more specific embodiments,at most 1% by weight and in yet more specific embodiments, at most 0.1%by weight, of the total amount of all of the substances present in thereaction space during the reaction.

In simple terms, in one specific embodiment, apart from the substanceswhich introduce the hydrophilic and/or hydrophobic sections into thepolyurethanes, the reaction products, if appropriate small amounts ofwater and the catalysts, the reaction mixture comprises no furthersubstances.

The specific process in which, apart from the starting materials for thepolyurethane formation, no further solvents are used, leads to a morerapid reaction and solvents do not have to be separated off.

A further advantage of dispensing with solvents, in particular organicsolvents which are different from the substances which introduce thehydrophilic and/or hydrophobic sections into the polyurethanes or whichact as catalyst, is the better acceptance of the resulting polyurethanesas ingredients of cosmetic preparations.

If solvents are nevertheless used in the process according to one ormore embodiments of the invention which are different from thesubstances which introduce the hydrophilic and/or hydrophobic sectionsinto the polyurethanes or which act as catalyst, then these are removedas far as possible after the reaction. “After the reaction” means thepoint at which the content of isocyanate groups is at most still 0.1% byweight, based on the total weight of the reaction mixture.

Single-Stage Process

In a specific embodiment, the process is carried out as a single-stageprocess.

“Single-stage” means here that the substances with groups reactivetowards isocyanate groups are essentially brought into contact togetherand simultaneously with the substances carrying isocyanate groups.

In one specific embodiment of the invention, a mixture of the substanceswith groups reactive towards isocyanate groups is thus brought intocontact with the substances carrying isocyanate groups.

In this case, it is possible for the entire amount of all of thesubstances with groups reactive towards isocyanate groups to be broughtinto contact with the substances carrying isocyanate groups right at thestart of the reaction in the reaction space. Such a procedure isdescribed, for example, in example 10 of EP 761780 A2 on p. 14, lines 29to 47 and the following examples 11 to 24.

One characteristic of the single-stage process is that all types ofsubstances with groups reactive towards isocyanate groups are presentalongside one another at every point in the reaction. However, it is notobligatory that the quantitative ratio of the different substances inthe mixture is constant.

In the case of the single-stage reaction as opposed to the two-stagereaction, the polyol is not firstly brought into contact with an excessof polyisocyanate, giving prepolymers of the structure -D-P-D- and-D-P-D-P-D- with isocyanate chain ends, and these being reacted in thesecond step with the ethoxylated alcohol, then giving the structuresT-S-D-P-D-S-T or T-S-D-P-D-P-D-S-T.

In the specific embodiments of single-stage reaction, from the start, aswell as structures T-S-D-P-D-S-T and T-S-D-P-D-P-D-S-T, also structuresT-S-D-S-T are formed.

However, for the single-stage process, it is not obligatory that theentire amounts of all of the substances with groups reactive towardsisocyanate groups are already provided in the reaction space at thestart of the reaction. It is also conceivable that, at the start of thereaction, only in each case some of each substance with groups reactivetowards isocyanate groups are provided in the reaction space and theremainder of the substances in each case is added during the reaction.

In the two-stage process, in the first stage, the majority of thesubstances with two or more groups reactive towards isocyanate isbrought into contact with the substances carrying isocyanate groups, andthe substances with only one group reactive towards isocyanate groupsreact in the second stage with the remaining isocyanate groups and formthe chain ends of the polyurethanes.

In the single-stage process, the amount of polymers with the structureT-S-D-S-T is larger than in the two-stage process, whereas in thetwo-stage process the amount of polymers with the structureT-S-D-P-D-S-T is greater.

In one specific embodiment, the polyurethanes prepared by the processaccording to one or more embodiments of the invention are transferred toan aqueous phase, optionally after solvents have been separated off.

It is advantageous to stabilize the aqueous mixture obtained aftertransferring the reaction products to water.

Suitable free-radical scavengers are for example hydroxy-TEMPO,2,6-di-tert-butyl-p-kresol (Kerobit® TBK), hydroquinone monomethylether, tocopherol and mixtures of these compounds. These stabilizers areused in an amount in the range from 5-500 ppm, based on the weight ofthe aqueous mixture.

It is also advantageous to use preservatives. Of suitability are, forexample, phenoxyethanol, methylisothiazolinone, ethylhexylglycerol,3-acetyl-6-methyl-2H-pyran-2,4(3H)-dione, benzoic acid, parabens andmixtures of these substances. The preservatives are used in amounts inthe range from 0.1 to 1% by weight, based on the aqueous mixture.

In certain specific embodiments, substances with groups reactive towardsisocyanate groups are used in the process according to one or moreembodiments of the invention that are essentially water-free in order toprevent a competing reaction of the isocyanate groups with water. Thewater can be separated off from these substances in the processaccording to one or more embodiments of the invention by azeotropicdistillation, drying in vacuo or other methods known to the personskilled in the art. For example, the water is removed up to a watercontent of the substances of at most 500 ppm, and in some embodiments,at most 300 ppm.

The preparation of the actual reaction can for example involve exposingthe substances with groups reactive towards isocyanate groups to reducedpressure, and in some embodiments, vacuum, and thus largely removing thewater.

The water-comprising substances can also be mixed with a solvent such asxylene, toluene or acetone and the water can be removed together withthe added solvent by azeotropic distillation.

In the process according to one or more embodiments of the invention,the ratio (mol to mol) of the polyetherdiols used to diisocyanates usedcan be in the range from 1:1.1 to 1:2. In certain specific embodiments,the ratio is in the range from 1:1.1 to 1:1.9. The ratio is, in specificembodiments, in the range from 1:1.1 to 1:1.8. The ratio is especially,in specific embodiments, in the range from 1:1.2 to 1:1.75. The ratiocan of course also be 1:x where x is greater than or equal to 1.3, andin some embodiments, x is greater than or equal to 1.5.

In one embodiment, this results in no, one or two sections P, inspecific embodiments, being present in one molecule of the polyurethanesobtainable according to the invention.

In one embodiment of the process according to one or more embodiments ofthe invention, in addition to the stated ranges of the ratio ofpolyetherdiols to diisocyanates, the ratio of polyetherdiols toethoxylated alcohols is additionally chosen such that the molarquantitative ratio of polyetherdiols used to ethoxylated alcohols usedis in the range from 5:1 to 1:2. In certain specific embodiments, thisratio is in the range from 2:1 to 1:2, in specific embodiments, in therange from 1.5:1 to 1:2, and in even more specific embodiments, about1:1.

For a specific process according to one or more embodiments of theinvention, it is the case that a molar quantitative ratio ofpolyetherdiols to diisocyanates to ethoxylated alcohols of 1:1.2 to1:75:1 to 2 and in particular 1:1.5:1 is used.

The invention also provides the process, according to one or moreembodiments of the invention, wherein in each case at least onealkoxylated C₄-C₃₀-alcohol, one polyetherdiol and one diisocyanate areused for preparing the polyurethanes.

In a specific embodiment, is given to such a process wherein at leastone C₄-C₃₀-alcohol is a branched C₁₂-C₃₀-alkanol, at least onepolyetherdiol has a molecular weight M_(n) in the range from 4000 to 12000 g/mol and at least one diisocyanate is an aliphatic diisocyanate.

Yet another aspect of the invention also relates to the use of thepolyurethanes according to the invention for preparing aqueouspreparations. In specific embodiments, preparations may comprise atleast 5% by weight, in particular at least 20% by weight, in veryspecific embodiments at least 30% by weight and most, in yet morespecific embodiments, at least 70% by weight, of water.

In specific embodiments, the preparations may comprise at most 95% byweight, in specific embodiments, at most 90% by weight and in particularat most 85% by weight, of water.

The preparations comprising water are, for example, solutions,emulsions, suspensions or dispersions.

In addition to the polyurethanes obtainable by the process according toone or more embodiments of the invention, it is possible to use furthersubstances for preparing the preparations, such as e.g. customaryauxiliaries (for example dispersants and/or stabilizers), surfactants,preservatives, antifoams, fragrances, wetting agents, UV filters,pigments, emollients, active ingredients, further thickeners, dyes,softeners, humectants and/or other polymers.

The polyurethanes obtainable by the process according to one or moreembodiments of the invention and mixtures thereof are, in specificembodiments, used for effectively and stably thickening preparationswith a content of salts and pigments of more than 1% by weight, based onthe preparation. Here, “stably” means maintaining an increased viscositycompared with the unthickened state over a period of several weeksand/or when increasing the temperature of the preparation, for exampleto up to 50° C.

The polyurethanes obtainable by the process according to one or moreembodiments of the invention exhibit their thickening effect even atelevated temperatures up to about 50° C.

Furthermore, the polyurethanes obtainable by the process according toone or more embodiments of the invention exhibit a thickening effect ina broad pH from 2 to 13.

The polyurethanes obtainable by the process according to one or moreembodiments of the invention furthermore have an influence on thestructure of the preparations in which they enlarge the finely dividednature of the particles dispersed therein, i.e. reduce the particlesize.

The polyurethanes obtainable by the process according to one or moreembodiments of the invention and mixtures thereof can also be used forpreparing water-comprising preparations which comprise at least one saltor at least one surfactant or mixtures thereof.

In connection with the present invention, surfactants are alsounderstood as meaning emulsifiers and also mixtures of surfactants andemulsifiers. In connection with the present invention, salt isunderstood as meaning salts and also salt-like structures also with alow pK_(a) value and mixtures thereof.

The polyurethanes obtainable according to the invention are, in specificembodiments, used in order to prepare preparations which comprise atleast 0.05% by weight of salt and/or at least 0.5% by weight ofsurfactants, in very specific embodiments comprising at least 0.1% (w/w)of salt and/or at least 1% by weight of surfactants.

In a further embodiment, the polyurethanes obtainable by the processaccording to one or more embodiments of the invention are used forpreparing preparations which comprise at least 5% by weight, and in someembodiments, at least 10% by weight, of salt.

In a further embodiment, the polyurethanes obtainable by the processaccording to one or more embodiments of the invention are used forpreparing preparations which comprise up to 25% by weight ofsurfactants, and in some embodiments, up to 20% by weight and, inspecific embodiments, 15% by weight or fewer surfactants.

In a further embodiment, the polyurethanes obtainable by the processaccording to one or more embodiments of the invention are used forpreparing preparations which comprise at least 1% by weight of salt andup to 20% by weight of surfactants, and in some embodiments, up to 15%by weight of surfactants.

The polyurethanes obtainable by the process according to one or moreembodiments of the invention are used for preparing preparations whichare oil-in-water emulsions.

Typically, oil-in-water emulsions comprise oil in the range from morethan 0 to 40% by weight. In certain specific embodiments, according tothe invention, oil-in-water emulsions are prepared which comprise an oilfraction in the range from 5 to 40% by weight, particularly in the rangefrom 10 to 35% by weight and in particular from 15 to 30% by weight, ofoil.

The polyurethanes obtainable by the process according to one or moreembodiments of the invention are in very specific embodiments used forpreparing preparations which are oil-in-water emulsions and moreovercomprise at least one salt.

The preparations according to the invention which comprise apolyurethane obtainable by the process according to one or moreembodiments of the invention may be, for example, solutions, emulsions,suspensions or dispersions.

In one embodiment, a preparation according to the invention is adispersion, and in some embodiments, an aqueous dispersion of thepolyurethanes obtainable by the process according to one or moreembodiments of the invention, as can be obtained from the reactionproducts by work-up after the preparation process. For this, forexample, water is added to the reaction mixture after the reaction toproduce a dispersion. If desired, the addition of a preservative and/orstabilizer can also take place.

In one embodiment, a dispersion according to the invention comprises upto 50% by weight of the polyurethanes obtainable according to theinvention.

In another embodiment, a dispersion according to the invention comprises25% by weight solids fraction.

In a specific embodiment, the aqueous dispersions comprise up to 25% byweight of the polyurethanes obtainable according to the invention, atleast one of the above-described preservatives suitable for cosmeticapplications and, if desired, at least one of the above-describedstabilizers suitable for cosmetic applications.

In another embodiment, the polyurethane obtainable according to theinvention is in the form of a powder. Such a powder can be obtained, forexample, by spray-drying or freeze-drying the aqueous dispersion.

To prepare the preparations according to the invention, which may be,for example, solutions, emulsions, suspensions or dispersions, thepolyurethanes according to the invention are, in specific embodiments,used in the form of aqueous dispersions or as a powder, as can beobtained, for example, from the preparation process by appropriatework-up.

Further ingredients may be present in the preparations according to theinvention depending on the intended use.

The preparations comprising the polyurethanes according to the inventioncan comprise further thickeners. Such further thickeners are known tothe person skilled in the art. Suitable thickeners are specified forexample in “Kosmetik and Hygiene von Kopf bis Fuβ [Cosmetics and Hygienefrom Head to Toe]”, Ed. W. Umbach, 3rd edition, Wiley-VCH, 2004, pp.235-236. Suitable further thickeners for the preparations according tothe invention are described for example also on page 37, line 12 to page38, line 8 of WO 2006/106140. Reference is hereby made to the contentsof the cited passages in their entirety.

In one embodiment of this invention, however, no further thickeners areused besides the polyurethanes according to the invention for preparingthe preparations according to the invention.

In specific embodiments of the polyurethanes according to the invention,the 10% strength by weight aqueous dispersions thereof having, at ashear rate of 100 l/s, a dynamic viscosity (measured as described below)of at least 100 mPa*s, in specific embodiments, of at least 200 mPa*sand in very specific embodiments of at least 300 mPa*s.

The aqueous dispersions of the polyurethanes obtainable by the processaccording to one or more embodiments of the invention can in this caseeither exhibit Newtonian or else non-Newtonian behavior. Non-Newtonian10% strength by weight aqueous dispersions which comprise thepolyurethanes obtainable by the process according to one or moreembodiments of the invention have, at a shear rate of 100 l/s, dynamicviscosities of at least 1000 mPa*s, in specific embodiments, of at least3000 mPa*s.

The person skilled in the art is aware that, in water-comprisingpreparations, many thickeners lose their effectiveness, i.e. theviscosity of the preparation decreases, as soon as the preparationscomprise salts or surfactants. By contrast, the polyurethanes accordingto the invention permit a stable viscosity of aqueous preparations evenupon the addition of salts and/or surfactants.

Certain embodiments relate to polyurethanes according to the inventionwhich, in the case of a salt concentration of at least 0.5% by weightfollowing the addition, lead to a stabilization of the dynamicviscosity, measured as described below, of the aqueous preparationscomprising them.

Certain embodiments relate to those polyurethanes which permit a stabledynamic viscosity even upon the addition of at least 0.5% by weight ofsalt and addition of at least 1% by weight of surfactant.

In a further embodiment, the presence of the polyurethanes according tothe invention in salt-containing aqueous preparations leads to anincrease in the viscosity compared to preparations which comprise onlysalt or only polyurethanes according to the invention.

The order in which polyurethane and salt are added is irrelevant in thiscase.

Certain embodiments relate to polyurethanes according to the inventionwhich lead to an increase in the dynamic viscosity of aqueous salt-and/or surfactant-containing preparations.

Polyurethanes according to the invention which, in the case of a saltconcentration of the aqueous preparation of at least 0.05% by weightlead to an increase in the dynamic viscosity of the aqueous solutionaccording to specific embodiments.

Polyurethanes according to specific embodiments of the invention, in thecase of a salt concentration of greater than or equal to 0.5% by weightlead to an increase in the dynamic viscosity of the aqueouspreparations. In certain specific embodiments, the polyurethanesprepared are those which lead to an increase in the dynamic viscositycompared to preparations which comprise less than 0.05% by weight, andin some embodiments, less than or equal to 0.01% by weight, of salt, orless than 0.5% by weight, and in some embodiments, less than or equal to0.1% by weight, of surfactant.

A further advantage of the polyurethanes obtainable by the processaccording to one or more embodiments of the invention is the micelleformation in water. The critical material concentration for micelleformation, also called critical micelle concentration (CMC) indicatesthe concentration of a substance, in most cases of a substance which hashydrophobic and hydrophilic sections on the inside, at which micelleswith an average particle size of less than or equal to 200 nm, inparticular less than or equal to 100 nm (determinable by means ofdynamic light scattering as described herein below) are spontaneouslyformed. The CMC of the polyurethanes according to the invention inwater, determined as described herein below, is, in specificembodiments, less than or equal to 1 g/l, in specific embodiments, lessthan or equal to 0.5 g/l, in even more specific embodiments, less thanor equal to 0.25 g/l and in very specific embodiments less than or equalto 0.1 g/l.

A further advantage of the process according to one or more embodimentsof the invention, of the polyurethanes obtainable thereby and of thepreparations according to one or more embodiments of the invention isthe use of alkali(ne earth) metal carboxylate catalysts and thus thesimultaneous omission of cosmetically unacceptable catalysts during thepreparation of the polyurethanes.

In the field of cosmetic preparations, the known processes with tin areno longer desired since tin may also be present in the products andpreparations resulting therefrom.

The use of the alkali(ne earth) metal carboxylates as catalysts for theprocess according to one or more embodiments of the invention permitsthe in-situ production of allophanate and isocyanurate structures andthus the economically advantageous production of branched hydrophobicsections D of the polyurethanes. By virtue of partially branchedsections D, polyurethane thickeners with higher efficiency can beobtained.

On account of their tolerance toward high salt contents andsimultaneously high surfactant contents even at extreme pH values, thepolyurethanes according to the invention can advantageously also be usedas thickeners in homecare preparations, such as, for example, liquidcleaners.

In particular, the polyurethanes according to the invention are alsosuitable as rheology modifiers for preparations containing hydrogenperoxide.

Cosmetic Preparations

The polyurethanes obtainable according to the invention are, in specificembodiments, used in cosmetic preparations. The invention thus providescosmetic preparations comprising the polyurethanes obtainable accordingto the invention.

One embodiment of the invention is water-comprising cosmeticpreparations comprising polyurethanes obtainable according to theinvention.

The preparations according to the invention can be in the form ofaqueous or aqueous-alcoholic solutions, O/W and W/O emulsions,hydrodispersion formulations, solids-stabilized formulations, stickformulations, PIT formulations, in the form of creams, foams, sprays(pump spray or aerosol), gels, gel sprays, lotions, oils, oil gels ormousses and accordingly be formulated with customary furtherauxiliaries.

In certain specific embodiments, the preparations according to theinvention are in the form of a gel, foam, mousse, spray, ointment,cream, emulsion, suspension, lotion, milk or paste.

The invention, in specific embodiments, relates to cosmetic preparationswhich are selected from gels, gel creams, milks, hydroformulations,stick formulations, cosmetic oils and oil gels, mascara, self-tanningcompositions, face care compositions, body care compositions, aftersunpreparations. The term cosmetic preparations is also understood asmeaning preparations for oral care.

Further cosmetic preparations according to the invention are skincosmetic preparations, in particular those for caring for the skin.These are present in particular as W/O or, in other embodiments, O/Wskin creams, day and night creams, eye creams, face creams, antiwrinklecreams, mimic creams, moisturizing creams, bleaching creams, vitamincreams, skin lotions, care lotions and moisturizing lotions.

Further specific preparations according to embodiments of the inventionare face masks, cosmetic lotions and preparations for the use indecorative cosmetics, for example for concealing sticks, stage make-up,mascara and eyeshadows, lipsticks, kohl pencils, eyeliners, make-ups,foundations, blushers, powders and eyebrow pencils.

Further preparations according to the invention are antiacnecompositions, repellents, shaving compositions, hair removalcompositions, intimate care compositions, foot care compositions andbaby care products.

Further specific preparations according to embodiments of the inventionare washing, showering and bathing preparations. Within the context ofthis invention, washing, showering and bathing preparations are soaps ofliquid to gel-like consistency, transparent soaps, luxury soaps,deodorant soaps, cream soaps, baby soaps, skin protection soaps,abrasive soaps and syndets, pasty soaps, soft soaps and washing pastes,liquid washing, showering and bathing preparations, such as washinglotions, shower baths and shower gels, foam baths, oil baths and scrubpreparations, shaving foams, shaving lotions and shaving creams.

Cosmetic preparations which comprise specific polyurethanes aredescribed for example in WO 2009/135857. The polyurethanes obtainableaccording to various embodiments of the invention are generally alsosuitable for use in the preparations described in WO 2009/135857.Reference is hereby made expressly to the disclosure in WO 2009/135857.

Within the context of the present invention, the polyurethanes used inthe preparations of WO 2009/135857 are replaced by the polyurethanes ofthis invention. The polyurethanes according to the invention are thusused in the preparations of WO 2009/135857, and in specific embodiments,in place of the polyurethanes used therein.

Suitable ingredients for the preparations according to the invention aredescribed in WO 2009/135857, p. 24 to p. 35, to which reference is madein its entirety.

By way of example cosmetic UV photoprotective compositions comprisingthe polyurethanes obtained according to the invention are in accordancewith the invention. Within the context of this invention, cosmeticphotoprotective compositions are understood as meaning cosmeticpreparations which comprise at least one, and in some embodiments, twoor more, UV filter substances.

UV photoprotective compositions corresponding to the UV photoprotectivecomposition preparations according to the invention are described in WO2009/135857, p. 35 to p. 42, to which reference is made in its entirety.

The invention also relates to cosmetic preparations, and in someembodiments, in liquid or pasty form, for use on the skin, on semimucosa, on mucosa and in particular on keratin materials such as hair,eyelashes and eyebrows, in particular for the shaping, decoration,coloring, beautifying of the same, and also for caring for the skin andthe skin appendages. In principle, the preparations according to theinvention, upon suitable adjustment and coloring, can also be used asmake-up, concealer, camouflage, eyeshadows, eyeliners, lip liners,blushers, lip blush, lip gloss, sun protection composition, sun block,temporary tattoo, colored effect sunscreen for surfers and the like.

A specific embodiment of the present invention is thus cosmeticpreparations for decorative cosmetics.

Preparations corresponding to the preparations according to theinvention for decorative cosmetics are described in WO 2009/135857, p.43 to p. 46, to which reference is made in its entirety.

Various embodiments of the present invention provide aqueouspreparations which, besides the polyurethanes obtainable according tothe invention, further comprise at least one salt or surfactant or both.

A further embodiment of the invention is shampoos and cosmetic cleaningcompositions comprising the polyurethanes obtainable according to theinvention.

Preparations corresponding to the shampoos and cosmetic cleaningcompositions according to the invention are described analogously in WO2009/135857, p. 46 to p. 55, to which reference is made in its entirety.

A further embodiment of the invention is deodorants or antiperspirants,in particular deodorant lotions and deodorant or antiperspirant sticks,comprising the polyurethanes obtainable according to the invention andbased on oil-in-water dispersion or emulsion for the application ofactive ingredients, in particular of water-soluble active ingredients,to the skin.

Preparations corresponding to the deodorants and antiperspirantsaccording to the invention are described analogously in WO 2009/135857,p. 55 to p. 59, to which reference is made in its entirety.

A further embodiment of the invention is hair colorants comprising thepolyurethanes obtainable according to the invention.

Preparations corresponding to the hair colorants comprising thepolyurethanes obtainable according to the invention are describedanalogously in WO 2009/135857, p. 59 to p. 65, to which reference ismade in its entirety.

A further embodiment of the invention is hair care compositions, inparticular hair conditioners, comprising the polyurethanes obtainableaccording to the invention.

Hair care compositions corresponding to the hair care compositionscomprising the polyurethanes obtainable according to the invention aredescribed analogously in WO 2009/135857, p. 59 to p. 67, to whichreference is made in its entirety.

A further embodiment of the invention is acidic preparations comprisingthe polyurethanes obtainable according to the invention.

Numerous cosmetic preparations comprise active ingredients which developtheir desired effect in particular at acidic pHs. These include, forexample, preparations which comprise alpha-hydroxycarboxylic acids(AHAs) and beta-hydroxycarboxylic acids (BHAs) since these are noteffective or not very effective in the neutralized state. Acidicpreparations corresponding to the acidic preparations comprising thepolyurethanes obtainable according to the invention are describedanalogously in WO 2009/135857, p. 67 to p. 69, to which reference ismade in its entirety.

A further embodiment of the invention is self-tanning productscomprising the polyurethanes obtainable according to the invention.

Standard commercial self-tanning products are generally O/W emulsions.In these, the water phase is stabilized by emulsifiers customary incosmetics.

By applying the self-tanning products according to the invention, it ispossible to achieve not only a uniform skin coloration, but it is alsopossible to uniformly color areas of skin that are differently coloredby nature or as a result of a pathological change.

According to the invention, the self-tanning substances used areadvantageously inter alia glycerol aldehyde, hydroxymethylglyoxal,γ-dialdehyde, erythrulose, 5-hydroxy-1,4-naphtoquinone (juglone), andalso 2-hydroxy-1,4-naphtoquinine as occurs in henna leaves. In veryspecific embodiments, the self-tanning substance compirses1,3-dihydroxyacetone (DHA), a trivalent sugar which occurs in the humanbody. 6-Aldo-D-fructose and ninhydrin can also be used as self-tanningagents according to the invention. For the purposes of the invention,self-tanning agents are also understood as meaning substances whichbring about a skin coloration other than a brown shade.

In one specific embodiment of the invention, such preparations compriseself-tanning substances in a concentration of from 0.1 to 10% by weightand, in specific embodiments, from 0.5 to 6% by weight, in each casebased on the total weight of the preparation.

In certain specific embodiments, these preparations comprise1,3-dihydroxyacetone as self-tanning substance. These compositionsfurther, and in some embodiments, comprise organic and/or inorganiclight protection filters. The preparations can also comprise inorganicand/or organic and/or modified inorganic pigments.

Further ingredients which, in certain embodiments, may be present in thepreparations according to the invention are specified, for example, inDE 103 21 147 in paragraphs [0024] to [0132], to which reference is madeat this point in their entirety.

The invention also provides the use of such preparations for coloringthe skin of multicellular organisms, in particular the skin of humansand animals, especially for harmonizing the color of differentlypigmented areas of skin.

A further embodiment of the invention is preparations for oral anddental care and cleansing which comprise the polyurethanes obtainableaccording to the invention.

Preparations corresponding to the preparations for oral and dental careand cleansing comprising the polyurethanes obtainable according to theinvention are described analogously in WO 2009/135857, p. 69 to p. 70,to which reference is made in its entirety.

A further embodiment of the invention is preparations for hair removalwhich comprise the polyurethanes obtainable according to the invention.

Preparations corresponding to the preparations for hair removal whichcomprise the polyurethanes obtainable according to the invention aredescribed analogously in WO 2009/135857, p. 70 to p. 71, to whichreference is made in its entirety.

A further embodiment of the invention is preparations for permanent hairshaping comprising the polyurethanes obtainable according to theinvention.

Preparations corresponding to the preparations for permanent hairshaping which comprise the polyurethanes obtainable according to theinvention are described analogously in WO 2009/135857, p. 71 to p. 73,to which reference is made in its entirety.

EXAMPLES

The invention is illustrated in more detail by reference to thenonlimiting examples below.

Unless stated otherwise, the percentages are percentages by weight.

Determination of the Dynamic Viscosity

The dynamic viscosities of the polyurethanes according to the inventionwere measured in each case in a 10% strength by weight aqueous solutionat 23° C. In the examples listed below, the dynamic viscosity was alwaysdetermined at shear rates of 100 l/s and 350 l/s. These two values allowa statement about whether the polyurethanes according to the inventionexhibit non-Newtonian or Newtonian thickener behavior in aqueousdispersion.

To determine the dynamic viscosity to DIN 53019, the following wereused:

-   -   rotary viscometer Physica Rheolab MC1 Portable (Anton Paar);    -   cylinder measurement system, Z4 DIN cylinder (diameter 14 mm).

The polyols, ethoxylated alcohols and isocyanates used below were usedin essentially alkali-free form (potassium content<5 ppm).

Synthesis Example 1 Preparation of a PUR Associative Thickener A.1Catalyst: 300 ppm of K as Potassium Acetate

120.00 g of polyethylene glycol Pluriol®E6000 (BASF SE, molecular weight6000 g/mol), 9.60 g of Lutensol®TO10 (BASF SE), 11.10 g of Lutensol®AT11(BASF SE), and 106 mg of potassium acetate (=300 ppm of potassium basedon total mixture) were introduced as initial charge under nitrogen in a2 liter polymerization reactor and then heated to 100° C. By applying avacuum of ca. 10 mbar for 6 hours, traces of water were removed untilultimately the water content of the mixture was 230 ppm. The mixture wasthen cooled to 80° C. By adding 5.88 g of hexamethylene diisocyanate,the polymerization was started and the mixture was stirred at atemperature of 80° C. for 50 minutes until an isocyanate content of 0.0%was reached. The yellow colored residue was then dissolved in 586.3 g ofwater and the aqueous solution was immediately admixed with 7.33 g ofEuxyl®K701 (Schülke & Mayr) and 70 mg of the stabilizer 4-hydroxy-TEMPO.The mixture was cooled to room temperature (25° C.). The polymer A.1(M_(n)=11 700 g/mol; M_(w)=26 900 g/mol) was thus obtained in the formof a clear, pale yellow colored solution which had a solids content of20.8%. The viscosity of a 10% strength by weight aqueous solution of thepolyether polyurethane A.1 was 1550 mPa*s (shear rate 100 l/s) and 1360mPa*s (shear rate 350 l/s).

Synthesis Example 2 Preparation of a PUR Associative Thickener A.2Catalyst: 600 ppm of K as Potassium Acetate

120.00 g of polyethylene glycol Pluriol®E6000, 9.60 g of Lutensol®TO10,11.10 g of Lutensol®AT11, and 212 mg of potassium acetate (=600 ppm ofpotassium based on total mixture) were introduced as initial chargeunder nitrogen in a 2 l polymerization reactor and then heated to 100°C. By applying a vacuum of ca. 10 mbar for 5 hours, traces of water wereremoved until ultimately the water content of the mixture was 225 ppm.The mixture was then cooled to 80° C. By adding 5.88 g of hexamethylenediisocyanate, the polymerization was started and the mixture was stirredat a temperature of 80° C. for 50 minutes until an isocyanate content of0.0% was reached. The yellow colored residue was then dissolved in 586.3g of water and the aqueous solution was immediately admixed with 7.33 gof Euxyl®K701 and 70 mg of the stabilizer 4-hydroxy-TEMPO. The mixturewas cooled to room temperature (25° C.). The polymer A.2 (M_(n)=12 300g/mol; M_(w)=29 700 g/mol) was thus obtained in the form of a clear,pale yellow colored solution which had a solids content of 20.1%. Theviscosity of a 10% strength by weight aqueous solution of the polyetherpolyurethane A.2 was 3700 mPa*s (shear rate 100 l/s) and 3000 mPa*s(shear rate 350 l/s).

Synthesis Example 3 Preparation of a PUR Associative Thickener A.3Catalyst: 900 ppm of K as Potassium Acetate

120.00 g of polyethylene glycol Pluriol®E6000, 9.60 g of Lutensol®TO10,11.10 g of Lutensol®AT11, and 318 mg of potassium acetate (=900 ppm ofpotassium based on total mixture) were introduced as initial chargeunder nitrogen in a 2 l polymerization reactor and then heated to 100°C. By applying a vacuum of ca. 10 mbar for 4 hours, traces of water wereremoved until ultimately the water content of the mixture was 242 ppm.The mixture was then cooled to 80° C. By adding 5.88 g of hexamethylenediisocyanate, the polymerization was started and the mixture was stirredat a temperature of 80° C. for 55 minutes until an isocyanate content of0.0% was reached. The yellow colored residue was then dissolved in 586.3g of water and the aqueous solution was immediately admixed with 7.33 gof the preservative Euxyl®K701 and 70 mg of the stabilizer4-hydroxy-TEMPO. The mixture was cooled to room temperature (25° C.).The polymer A.3 (M_(n)=12 700 g/mol; M_(w)=33 000 g/mol) was thusobtained in the form of a clear, pale yellow colored solution which hada solids content of 20.6%. The viscosity of a 10% strength by weightaqueous solution of the polyether polyurethane A.3 was 6000 mPa*s (shearrate 100 l/s) and 4400 mPa*s (shear rate 350 l/s).

Synthesis Example 4 Preparation of a PUR Associative Thickener A.4Catalyst: 2000 ppm of K as Potassium Acetate

90.00 g of polyethylene glycol Pluriol®E6000, 7.20 g of Lutensol®TO10,8.33 g of Lutensol®AT11, and 530 mg of potassium acetate (=2000 ppm ofpotassium based on total mixture) were introduced as initial chargeunder nitrogen in a 2 l polymerization reactor and then heated to 100°C. By applying a vacuum of ca. 10 mbar for 5 hours, traces of water wereremoved until ultimately the water content of the mixture was 210 ppm.The mixture was then cooled to 80° C. By adding 4.41 g of hexamethylenediisocyanate, the polymerization was started and the mixture was stirredat a temperature of 80° C. for 55 minutes until an isocyanate content of0.0% was reached. The yellow colored residue was then dissolved in 439.7g of water and the aqueous solution was immediately admixed with 5.50 gof the preservative Euxyl®K701 and 50 mg of the stabilizer4-hydroxy-TEMPO. The mixture was cooled to room temperature (25° C.).The polymer A.4 (M_(n)=12 500 g/mol; M_(w)=31 300 g/mol) was thusobtained in the form of a clear, pale yellow colored solution which hada solids content of 20.6%. The viscosity of a 10% strength by weightaqueous solution of the polyether polyurethane A.4 was 5200 mPa*s (shearrate 100 l/s) and 3800 mPa*s (shear rate 350 l/s).

Synthesis Example 5 Preparation of a PUR Associative Thickener A.5Catalyst: 200 ppm of K as Potassium Acetate

100.00 g of polyethylene glycol (Merck KGaA, molecular weight 10 000g/mol), 10.02 g of 2-decyl-1-tetradecanol-20 EO, and 55 mg of potassiumacetate (=200 ppm of potassium based on total mixture) were introducedas initial charge under nitrogen in a 2 l polymerization reactor andthen heated to 100° C. By applying a vacuum of ca. 10 mbar for 6 hours,traces of water were removed until ultimately the water content of themixture was 190 ppm. The mixture was then cooled to 80° C. By adding2.52 g of hexamethylene diisocyanate, the polymerization was started andthe mixture was stirred at a temperature of 80° C. for 40 minutes untilan isocyanate content of 0.0% was reached. The yellow colored residuewas then dissolved in 450.2 g of water and the aqueous solution wasimmediately admixed with 5.63 g of the preservative Euxyl®K701 and 60 mgof the stabilizer 4-hydroxy-TEMPO. The mixture was cooled to roomtemperature (25° C.). The polymer A.5 (M_(n)=19 100 g/mol; M_(w)=48 500g/mol) was thus obtained in the form of a clear, pale yellow coloredsolution which had a solids content of 20.7%. The viscosity of a 5%strength by weight aqueous solution of the polyether polyurethane A.5was >20 000 mPa*s (shear rate 100 l/s) and >20 000 mPa*s (shear rate 350l/s).

Comparative Example 1 Preparation of a PUR Associative Thickener A.6Without Catalyst

120.00 g of polyethylene glycol Pluriol®E6000, 9.60 g of Lutensol®TO10,and 11.10 g of Lutensol®AT11 were introduced as initial charge undernitrogen in a 21 polymerization reactor and then heated to 100° C. Byapplying a vacuum of ca. 10 mbar for 5 hours, traces of water wereremoved until ultimately the water content of the mixture was 250 ppm.The mixture was then cooled to 80° C. By adding 5.88 g of hexamethylenediisocyanate, the polymerization was started and the mixture was stirredat a temperature of 80° C. for a total of 32 hours until an isocyanatecontent of 0.0% was reached. The yellow colored residue was thendissolved in 586.3 g of water and the aqueous solution was immediatelyadmixed with 7.33 g of the preservative Euxyl®K701 and 70 mg of thestabilizer 4-hydroxy-TEMPO. The mixture was cooled to room temperature(25° C.). The polymer A.6 (M_(n)=10 000 g/mol; M_(w)=23 200 g/mol) wasthus obtained in the form of a clear, pale yellow colored solution whichhad a solids content of 18.8%. The viscosity of a 10% strength by weightaqueous solution of the polyether polyurethane A.6 was 100 mPa*s (shearrate 100 l/s) and 100 mPa*s (shear rate 350 l/s).

Comparative Example 2 Preparation of a PUR Associative Thickener A.7Without Catalyst

100.00 g of polyethylene glycol (Merck KGaA, molecular weight 10 000g/mol), and 10.02 g of 2-decyl-1-tetradecanol-20 EO were introduced asinitial charge under nitrogen in a 2 l polymerization reactor and thenheated to 100° C. By applying a vacuum of ca. 10 mbar for 6 hours,traces of water were removed until ultimately the water content of themixture was 185 ppm. The mixture was then cooled to 80° C. By adding2.52 g of hexamethylene diisocyanate, the polymerization was started andthe mixture was stirred at a temperature of 80° C. for a total of 12hours until an isocyanate content of 0.0% was reached. The yellowcolored residue was then dissolved in 450.2 g of water and the aqueoussolution was immediately admixed with 5.63 g of the preservativeEuxyl®K701 and 60 mg of the stabilizer 4-hydroxy-TEMPO. The mixture wascooled to room temperature (25° C.). The polymer A.7 (M_(n)=5200 g/mol;M_(w)=14 500 g/mol) was thus obtained in the form of a clear, paleyellow colored solution which had a solids content of 18.5%. Theviscosity of a 10% strength by weight aqueous solution of the polyetherpolyurethane A.7 was <100 mPa*s (shear rate 100 l/s) and <100 mPa*s(shear rate 350 l/s).

Comparative Example 3 Preparation of a PUR Associative Thickener A.8Catalyst: Dibutyltin Dilaurate

90.00 g of polyethylene glycol Pluriol®E6000, 7.20 g of Lutensol®TO10,8.33 g of Lutensol®AT11, and 144 mg of dibutyltin dilaurate (DBTL) (=300ppm of Sn based on total mixture) were introduced as initial chargeunder nitrogen in a 2 l polymerization reactor and then heated to 100°C. By applying a vacuum of ca. 10 mbar for 5 hours, traces of water wereremoved until ultimately the water content of the mixture was 250 ppm.The mixture was then cooled to 80° C. By adding 4.41 g of hexamethylenediisocyanate, the polymerization was started and the mixture was stirredat a temperature of 80° C. for 60 minutes until an isocyanate content of0.0% was reached. The yellow colored residue was then dissolved in 440.3g of water and the aqueous solution was immediately admixed with 5.50 gof the preservative Euxyl®K701 and 60 mg of the stabilizer4-hydroxy-TEMPO. The mixture was cooled to room temperature (25° C.).The polymer A.8 (M_(n)=10 100 g/mol; M_(w)=22 000 g/mol) was thusobtained in the form of a clear, pale yellow colored solution which hada solids content of 20.4%. The viscosity of a 10% strength by weightaqueous solution of the polyether polyurethane A.8 was 720 mPa*s (shearrate 100 l/s) and 660 mPa*s (shear rate 350 l/s).

Comparative Example 4 Preparation of a PUR Associative Thickener A.9Catalyst: DABCO

120.00 g of polyethylene glycol Pluriol®E6000, 9.60 g of Lutensol®TO10,11.10 g of Lutensol®AT11, and 36 mg of 1,4-diazabicyclo[2.2.2]octane(DABCO; =300 ppm based on total mixture) were introduced as initialcharge under nitrogen in a 2 l polymerization reactor and then heated to100° C. By applying a vacuum of ca. 10 mbar for 5 hours, traces of waterwere removed until ultimately the water content of the mixture was 230ppm. The mixture was then cooled to 80° C. By adding 5.88 g ofhexamethylene diisocyanate, the polymerization was started and themixture was stirred at a temperature of 80° C. for a total of 13 hoursuntil an isocyanate content of 0.0% was reached. The yellow coloredresidue was then dissolved in 586.5 g of water and the aqueous solutionwas immediately admixed with 7.33 g of the preservative Euxyl®K701 and70 mg of the stabilizer 4-hydroxy-TEMPO. The mixture was cooled to roomtemperature (25° C.). The polymer A.9 (M_(n)=8500 g/mol; M_(w)=17 400g/mol) was thus obtained in the form of a clear, pale yellow coloredsolution which had a solids content of 18.7%. The viscosity of a 10%strength by weight aqueous solution of the polyether polyurethane A.9was 105 mPa*s (shear rate 100 l/s) and 105 mPa*s (shear rate 350 l/s).

Formulation Example 1 Cosmetic Formulations Based on Cremophor®A6/Cremophor® A25

The cosmetic formulations shown below were prepared by adding the waterphase B to the oil phase A and then admixing the resulting O/W emulsionwith the preservative (phase C). This gave the following formulationsbased on a Cremophor® A6/Cremophor® A25 base.

TABLE 1 Formulations based on Cremophor ® A6/Cremophor ® A25 PhaseIngredients F.1.1 F.1.2 F.1.3 F.1.4 F.1.6 F.1.8 Phase A Cremophor ® A 62.0 g 2.0 g 2.0 g 2.0 g 2.0 g 2.0 g Cremophor ® A 25 2.0 g 2.0 g 2.0 g2.0 g 2.0 g 2.0 g Lanette ® O 2.5 g 2.5 g 2.5 g 2.5 g 2.5 g 2.5 gParaffin oil 5.0 g 5.0 g 5.0 g 5.0 g 5.0 g 5.0 g Luvitol ® EHO 5.0 g 5.0g 5.0 g 5.0 g 5.0 g 5.0 g Phase B PUR thickener A.1 A.2 A.3 A.4 A.6 A.80.5 g 0.5 g 0.5 g 0.5 g 0.5 g 0.5 g 1,2-Propylene 5.0 g 5.0 g 5.0 g 5.0g 5.0 g 5.0 g glycol Water 77.5 g  77.5 g  77.5 g  77.5 g  77.5 g  77.5g  Phase C Euxyl ® K300 0.5 g 0.5 g 0.5 g 0.5 g 0.5 g 0.5 g

Formulation Example 2 Cosmetic Formulations Based on Stearate Ester

The following cosmetic formulations were prepared by adding the waterphase B to the oil phase A and subsequently admixing the resulting O/Wemulsion with the preservative (phase C). This gave the followingformulations based on a stearate ester base.

TABLE 2 Cosmetic formulations based on stearate ester Phase IngredientsF.2.1 F.2.2 F.2.3 F.2.4 F.2.6 F.2.8 Phase A Cutina ® GMS 2.0 g 2.0 g 2.0g 2.0 g 2.0 g 2.0 g Lanette ® 18 2.0 g 2.0 g 2.0 g 2.0 g 2.0 g 2.0 g DowCorning 345 Fluid 3.0 g 3.0 g 3.0 g 3.0 g 3.0 g 3.0 g Cetiol ® OE 3.0 g3.0 g 3.0 g 3.0 g 3.0 g 3.0 g Abil ® 350 2.0 g 2.0 g 2.0 g 2.0 g 2.0 g2.0 g Dry Flo PC 1.0 g 1.0 g 1.0 g 1.0 g 1.0 g 1.0 g Myrj 52 2.0 g 2.0 g2.0 g 2.0 g 2.0 g 2.0 g Phase B PUR thickener A.1 A.2 A.3 A.4 A.6 A.80.5 g 0.5 g 0.5 g 0.5 g 0.5 g 0.5 g Glycerol 5.0 g 5.0 g 5.0 g 5.0 g 5.0g 5.0 g Water 79.0 g  79.0 g  79.0 g  79.0 g  79.0 g  79.0 g  Phase CEuxyl ® K300 0.5 g 0.5 g 0.5 g 0.5 g 0.5 g 0.5 g

Viscosities of the Cosmetic Formulations F.1.1 to F.1.8 as a Function ofthe Salt Concentration

TABLE 3 Viscosity [mPa * s] Formulation with 2.0% NaCl addition F.1.1 12100 F.1.2 17 100 F.1.3 26 200 F.1.4 17 000 F.1.6   6800 F.1.8 11 400

Viscosities of the Cosmetic Formulations F.2.1-F.2.8 as a Function ofthe Salt Concentration

TABLE 4 Viscosity [mPa * s] Formulation with 2.0% NaCl addition F.2.1 16700 F.2.2 21 800 F.2.3 21 200 F.2.4 18 100 F.2.6 10 000 F.2.8 14 700

Viscosities of the Polyurethanes A.1-A.9 in Water, as a Function ofShear Rate and Concentration

TABLE 5 Polymer concentration Viscosity in water [mPa * s] Polymer [% byweight] Shear rate 100 1/s Shear rate 350 1/s A.1 10 1550 1360 A.2 103700 3000 A.3 10 6000 4400 A.4 10 5200 3800 A.5 5 >20 000     >20 000    A.6 10  100  100 A.7 10 <100 <100 A.8 10  720  660 A.9 10  105  105

FIG. 1 shows the GPC chromatograms of the polyurethanes A.5 and A.7.

The solid line in FIG. 1 represents A.5 (according to the invention, 200ppm of K as KOAc): high molar mass, and the dashed line represents A.7(not according to the invention, without KOAc): low molar mass.

Application Examples

At this point, reference is made in full to the application exampleswhich are disclosed in WO 2009/135857 on pages 87 to 114.

The polyurethanes PU.1 to PU.11 used in the examples therein arereplaced for the purposes of this invention by the polyurethanes A.1,A.2, A.3, A.4 or A.5 of the present invention, such that thecorresponding cosmetic preparations are obtained analogously.

Further typical preparations according to the invention are describedbelow, without, however, limiting the invention to these examples.

Besides the preparation of the cosmetic preparations described here, thepolyurethanes A.1, A.2, A.3, A.4 or A.5 and also combinations thereofcan be added to the resulting emulsion also after combining the waterphase and oil phase at 60-80° C. or to the cooled emulsion at about 40°C.

The invention also provides the subsequent addition of the polyurethanesobtainable according to the invention to a cosmetic preparation in orderto establish the desired viscosity.

Unless expressly described otherwise, the percentages are % by weight.

O/W Emulsion

Phase Ingredient/INCI F.3.1 F.3.2 F.3.3 F.3.4 F.3.5 A Aqua ad 100 ad 100ad 100 ad 100 ad 100 Glycerin 3.0 5.50 4.50 5.00 3.5 PUR thickener 3.01.5 0.8 2.0 2.5 A.1 Hydroxyethyl 1.0 0.5 Acrylate/SodiumAcryloyldimethyl Taurate Copolymer, Squalane, Polysorbate 60 B GlycerylStearate 1.80 2.00 3.00 1.50 2 Citrate Sucrose Stearate 1.00 1.20 2.002.20 1.5 Cetearyl Alcohol 1.80 2.00 1.50 2.40 2.8 Ethylhexyl 6.00 5.003.50 3.00 5.5 Palmitate Caprylic/Capric 5.00 5.00 1.00 2.00 3.5Triglyceride Octyldodecanol 1.50 3.00 2.40 5.0 4.6 Dimethicone 0.20 0.502.00 1.80 1.4 C Ammonium 0.5 0.1 Acryloyldi- methyltaurate/ VP CopolymerCarbomer 0.05 0.1 D Sodium 0.02 0.04 Hydroxide E Bisabolol 0.5 0.3 0.200.35 1.0 Phenoxyethanol, 1.00 0.60 0.70 0.60 0.5 paraben mixture Perfume0.05 0.10 0.10 0.05 0.05

Preparation:

Heat phases A and B separately to ca. 80° C. Stir phase C into phase Band then stir phase A into phase B/C and briefly homogenize.

Add phase D (when required) and cool with stirring to ca. 40° C. Addcomponents of phase E to the emulsion in succession and cool withstirring to room temperature. Briefly homogenize.

Instead of the O/W emulsion comprising polyurethane thickener A.1, O/Wemulsions comprising one or more of the polyurethanes A.2, A.3, A.4 orA.5 are also prepared.

Hydrodispersion

Phase Ingredients/INCI F.4.1 F.4.2 F.4.3 F.4.4 F.4.5 A Stearyl alcohol0.5 1.5 2.0 Cetyl alcohol 1.00 2.5 C12-15 Alkyl 2.5 4.0 benzoateDicapryl ether 4.0 6.0 Butylene glycol 4.0 2.0 1.0 dicaprylate/dicaprateDicapryl carbonate 2.0 3.0 4.0 Cyclopentasiloxane, 2.0 0.5cyclohexasiloxane Prunus Amygdalus 2.0 0.5 Dulcis (Sweet Almond) oilShea butter 2.0 1.0 Hydrogenated 3.0 1.0 7.0 0.5 2.0 polyisobuteneSqualane 2.0 0.5 Vitamin E acetate 0.50 0.25 1.00 B Acrylate/C10-30 0.30.1 0.2 0.15 0.2 alkyl acrylate crosspolymer C Aqua ad ad 100 ad 100 ad100 ad 100 100 Polyacrylamide, 1.0 1.5 0.75 C13-14 isoparaffin,Laureth-7 PUR thickener A.1 2.5 2.0 0.9 1.5 3.0 Propylene Glycol 3.005.0 2.5 7.50 10.0 D Sodium Hydroxide 0.12 0.04 0.08 0.06 0.08 ENiacinamide 0.30 3.0 1.5 0.5 0.20 Aqua 2.0 10.0 5.0 2.0 2.0 F DMDMHydantoin 0.60 0.45 0.25 Methylparaben 0.50 0.25 0.15 Phenoxyethanol0.50 0.40 1.00 Ethylhexylglycerin 1.00 0.80 Ethanol 3.00 2.00 1.50 7.00G Fragrance 0.20 0.05 0.40

Preparation:

Heat phases A and C separately to ca. 80° C.

Stir phase B into phase A and then phase C into phase A/B. Brieflyhomogenize. Add phase D and cool with stirring to ca. 40° C. Add phase Eand cool with stirring to ca. 30° C. Add phase F and G to the emulsionand cool to room temperature with stirring. Briefly homogenize.

Instead of the hydrodispersion comprising polyurethane thickener A.1,hydrodispersions comprising one or more of the polyurethanes A.2, A.3,A.4 or A.5 are also prepared.

Solids-Stabilized Emulsion

Phase Ingredients/INCI F.5.1 F.5.2 F.5.3 F.5.4 F.5.5 A Mineral oil 4.06.0 16.0 10.0 6.0 Octyldodecanol 9.0 9.0 5.0 Ethylhexyl 9.0 9.0 6.0 5.08.0 isononanoate Isohexadecane 9.0 5.0 4.0 8.0 Dimethicone 0.5 2.0 1.01.5 Cera 0.35 0.75 3.0 Microcristallina, Paraffinum Liquidum Phenyl 2.01.0 2.5 3.0 trimethicone Silica 2.5 6.0 2.5 Aluminum starch 2.0 1.0 0.5octenylsuccinate Tapioca starch 0.5 B Titanium dioxide, 1.0 0.5 3.0 2.04.0 coated Zinc oxide 5.0 10.0 2.0 3.0 C Ammonium 0.2 1.0 0.5Acryloyldi- methyltaurate/ Beheneth-25 Methacrylate Crosspolymer D Aquaad 100 ad 100 ad 100 ad 100 ad 100 Hydroxypropyl 0.1 0.05Methylcellulose Sorbitol 5.0 7.0 8.5 3.0 4.5 PUR thickener 3.0 5.0 0.91.4 2.0 A.1 E Mixed parabens 0.3 0.6 0.2 0.4 Phenoxyethanol 0.2 0.3 0.40.5 0.4 Diazolidinyl urea 0.23 0.2 F Perfume 0.2 0.3 0.1

Preparation:

Heat phase A to 80° C.

Add phase B to phase A and homogenize for 3 min. Stir in phase C.

Allow cellulose (if required) to preswell in water, then add theremaining ingredient of phase D and heat to 80° C.

Stir phase D into phase A+B+C and homogenize. Cool emulsion withstirring to ca. 40° C. and add phase E and F. With stirring, cool to RTand homogenize.

Instead of the solids-stabilized emulsion comprising polyurethanethickener A.1, solids-stabilized emulsions comprising one or more of thepolyurethanes A.2, A.3, A.4 or A.5 are also prepared.

Sunscreen Cream

Phase Ingredients/INCI F.6.1 F.6.2 F.6.3 F.6.4 F.6.5 A Aqua ad 100 ad100 ad 100 ad 100 ad 100 Disodium EDTA 0.1 0.1 0.1 0.1 0.1 Glycerin 3.007.50 8.0 7.50 5.00 Benzophenone-4 2.0 4.0 Phenyl- 0.50 4.00 8.0benzimidazole sulfonic acid Triethanolamine 1.0 0.25 2.0 2.0 4.0Panthenol 0.5 0.75 1.0 PUR thickener 2.5 g 0.5 g 2.0 g 4.0 1.5 A.1Xanthan gum 0.3 0.15 0.2 B Octocrylene 8.0 7.5 Ethylhexyl 5.0 10.0 8.03.0 7.0 methoxy- cinnamate, diethylamino hydroxybenzoyl hexyl benzoateSteareth-21 2.0 3.0 2.5 Steareth-2 1.5 PEG-40 stearate 1.0 2.0 Glycerin1.0 3.0 1.5 1.5 monostearate SE Dibutyl adipate 3.0 5.0 3.5 2.5 2.0Cetearyl alcohol 2.0 0.5 3.0 Stearyl alcohol 1.5 3.0 2.5 0.6 2.0Butyrospermum 1.0 0.5 1.0 1.5 Parkii (Shea Butter) Dimethicone 1.0 0.51.5 0.8 2.0 PVP hexadecene 0.20 0.50 0.8 1.00 copolymer Bisabolol 0.20.1 0.3 C DMDM 0.5 0.5 0.5 0.5 0.75 hydantoin Water, Aloe 0.5 1.0Barbadensis Leaf Juice Alpha- 0.60 0.5 0.4 0.25 0.3 glucosylrutinPerfume 0.10 0.25 0.30 0.40 0.20

Preparation:

Heat phases A and B separately to ca. 80° C.

Stir phase A into phase B and briefly homogenize.

Cool to ca. 40° C. with stirring. Add components of phase C to theemulsion in succession and cool to room temperature with stirring.Briefly homogenize.

Instead of the sunscreen cream comprising polyurethane thickener A.1,sunscreen creams comprising one or more of the polyurethanes A.2, A.3,A.4 or A.5 are also prepared.

Face Cream with Sodium Ascorbyl Phosphate

Phase Ingredients/INCI F.7.1 F.7.2 F.7.3 F.7.4 F.7.5 A Water ad 100 ad100 ad 100 ad 100 ad 100 Butylene glycol 5.0 6.5 5.5 3.5 4.0 PURthickener 3.5 1.5 2.5 5.0 2.0 A.1 Xanthan gum 0.25 0.2 0.1 Potassiumsorbate 0.1 0.1 0.1 0.1 0.1 Imidazolidinyl 0.3 0.2 urea B Potassium 1.52.0 1.9 2.5 1.0 cetyl phosphate Caprylic/capric 2.0 5.0 3.0 4.0 2.5triglyceride Stearyl alcohol 0.5 1.5 2.0 1.0 3.0 Cetearyl alcohol, 1.52.0 1.8 1.9 2.1 dicetyl phosphate, Ceteth-10 phosphate Simmondsia 3.01.5 0.5 1.0 2.5 Chinensis (Jojoba) seed oil Mineral oil 2.0 5.0 10.0 7.54.0 Paraben mixture 0.2 0.2 0.2 0.2 0.2 C Sodium ascorbyl 5.0 2.0 3.04.0 1.5 phosphate Lactic acid q.s. q.s. q.s. q.s. q.s. Water 10.0 4.05.0 10.0 3.0 D Tocopherol 0.1 0.2 Retinol 0.03 0.025 0.05 E Fragrance0.1 0.05 0.05 0.1 0.15

Preparation

Heat phases A and B separately to 80° C.

Stir phase A into phase B and homogenize.

Stir phase C into phase A+B and homogenize.

Cool to ca. 40° C. with stirring. Adjust pH of phase C to <6.5 withlactic acid. Add phase C and cool to ca. 30° C. with stirring. Add phaseD and E. Cool to room temperature with stirring and briefly homogenize.

Note: adjust pH of the emulsion to <6.5 with lactic acid.

Instead of the face cream comprising polyurethane thickener A.1, facecreams comprising one or more of the polyurethanes A.2, A.3, A.4 or A.5are also prepared.

Hydroxycarboxyclic Acid Cream

Phase Ingredients/INCI F.8.1 F.8.2 F.8.3 A Ceteareth-6, stearyl alcohol2.0 2.5 Ceteareth-25 2.0 2.5 PEG-100 stearate, glyceryl 3.5 0.5 stearatePolyglyceryl-3 distearate 2.0 Mineral oil 8.0 3.5 5.0 Cetearylethylhexanoate 7.0 5.5 4.0 Sorbitan stearate 0.5 1.5 0.5 Cera Alba 0.51.0 Cetyl alcohol 1.5 3.5 4.0 Dimethicone 0.2 2.0 0.5 B Panthenol 1.00.5 0.3 Propylene glycol 3.0 2.0 5.0 PUR thickener A.1 1.0 3.0 5.0Hydroxy acid 3.0 7.0 10.0  Aqua ad 100 ad 100 ad 100 C Sodium hydroxideq.s. q.s. q.s. D Bisabolol 0.2 0.1 0.3 Preservative q.s. q.s. q.s.Fragrance q.s. q.s. q.s. Note Alpha-hydroxy acids: lactic acid, citricacid, malic acid, glycolic acid Dihydroxy acid: tartaric acidBeta-hydroxy acid: salicylic acid Adjust pH to >3

Preparation

Heat phase A and B separately to ca. 80° C. Adjust pH of phase B to >3if necessary using NaOH. Stir phase B into phase A, briefly homogenize.

Cool to ca. 40° C. with stirring, add components of phase D insuccession, homogenize again.

Instead of the hydroxycarboxylic acid cream comprising polyurethanethickener A.1, hydroxycarboxylic acid creams comprising one or more ofthe polyurethanes A.2, A.3, A.4 or A.5 are also prepared.

Emulsion with deodorant active ingredient

Phase Ingredients/INCI F.9.1 F.9.2 F.9.3 F.9.4 F.9.5 Ceteareth-6,stearyl alcohol 1.5 2.0 1.0 Ceteareth-25 1.5 0.5 1.0 PEG-40 hydrogenatedcastor 0.5 1.0 2.0 oil Glyceryl stearate 0.5 2.0 1.0 Cetyl alcohol 2.01.0 0.5 2.5 0.2 Hydrogenated coco-glycerides 2.0 1.0 0.5 Hydrogenatedpolyisobutene 10.0 20.0 5.0 3.0 Decyl oleate 3.0 2.0 8.0 5.0Bis-PEG/PPG-14/14 3.0 3.5 4.0 2.0 1.5 dimethicone, cyclopentasiloxaneTalc 3.0 2.5 1.5 Magnesium aluminum silicate 1.0 0.5 1.0 1.5 B Propyleneglycol 10.0 5.0 7.5 20.0 15.0 PUR thickener A.1 0.5 1.0 3.0 3.5 2.0Xanthan gum 0.2 0.1 0.05 Cetyl hydroxyethylcellulose 0.3 0.1 Aluminumchlorohydrate 5.0 10.0 20.0 Aluminum zirconium 15.0 50.0 20.0tetrachlorohydrex GLY Aqua ad ad ad ad ad 100 100 100 100 100 CNeutralizing agent q.s. q.s. q.s. q.s. q.s. D Alcohol 5.0 10.0 25.0 7.56.0 Allantoin 0.1 0.1 0.1 0.1 0.1 Preservative q.s. q.s. q.s. q.s. q.s.Fragrance q.s. q.s. q.s. q.s. q.s.

Preparation

Heat phases A and B separately to ca. 80° C.

Stir phase B into phase A with homogenization. If appropriate, adjust topH 4-5 using phase C. Cool to ca. 40° C., add phase D and allow to coolto room temperature with stirring. Briefly homogenize.

Note: adjust pH of the emulsion to 4-5

Instead of the emulsion with deodorant active ingredient comprisingpolyurethane thickener A.1, emulsions with deodorant active ingredientcomprising one or more of the polyurethanes A.2, A.3, A.4 or A.5 arealso prepared.

Hair Removal Cream

Phase Ingredients/INCI F.10.1 F.10.2 F.10.3 A Glyceryl stearate 1.0Ceteareth-12 1.0 2.0 Ceteareth-20 1.0 2.0 Stearyl alcohol 4.0 1.0 Cetylalcohol 4.0 1.0 Mineral oil 6.0 4.0 Prunus Armeniaca 3.0 1.0 2.0(Apricot) kernel oil B Propylene glycol 1.0 2.0 10.0  Calcium carbonate10.0  Calcium hydroxide 7.0 Sodium hydroxide 0.4 0.6 Calciumthioglycolate 5.0 3.0 5.0 PUR thickener A.1 3.0 1.5 2.0 Aqua ad 100 ad100 ad 100 C Tocopherol 0.1 0.2 0.15 Bisabolol 0.2 0.1 0.3 Fragranceq.s. q.s. q.s.

Preparation

Heat phase A and B separately to ca. 80° C.

Stir phase B into phase A with homogenization, briefly homogenize.

Cool to ca. 40° C., add phase C, cool to RT with stirring and homogenizeagain.

Note: adjust pH of the emulsion to >10.

Instead of the hair removal cream comprising polyurethane thickener A.1,hair removal creams comprising one or more of the polyurethanes A.2,A.3, A.4 and A.5 are also prepared.

Self-Tanning Emulsion

Phase Ingredients/INCI F.11.1 F.11.2 F.11.3 F.11.4 A Isohexadecane 4.02.0 3.0 1.0 Dimethicone 1.0 1.0 0.5 1.5 Cetearyl alcohol 2.0 2.5 1.5 2.5Isopropyl myristate 1.0 2.0 3.0 Simmondsia Chinensis 2.0 1.0 0.5 0.5(Jojoba) seed oil Polyglyceryl-3 3.0 3.5 methylglucose distearate PEG-40stearate 2.5 2.0 Lecithin 0.5 1.0 Cetearyl glucoside 0.5 0.5 Sorbitanoleate 0.5 0.5 0.3 B Glycerin 4.0 5.0 Butylene glycol 4.0 3.0 PURthickener A.1 1.0 3.0 1.5 2.5 Xanthan gum 0.1 0.1 Aqua ad 100 ad 100 ad100 ad 100 C Dihydroxyacetone 1.5 5.0 Erythrulose 2.0 4.0 Aqua 5.0 10.0 5.0 8.0 Citric acid q.s. q.s. q.s. q.s. D Bisabolol 0.3 0.5 0.2 0.4Tocopheryl acetate 0.7 0.5 0.6 1.0 Preservative q.s. q.s. q.s. q.s.Fragrance q.s. q.s. q.s. q.s.

Preparation

Heat phases A and B separately to ca. 80° C.

Stir phase B into phase A and briefly homogenize.

With stirring, cool to ca. 40° C., add phase C and cool to 30° C. withstirring. Add components of phase D in succession and cool to RT withstirring. Briefly homogenize.

Note: adjust pH of the emulsion to 4-5.5

Instead of the self-tanning emulsion comprising polyurethane thickenerA.1, self-tanning emulsions comprising one or more of the polyurethanesA.2, A.3, A.4 or A.5 are also prepared.

Conditioner Shampoo

Ingredients/INCI F.12.1 F.12.2 F.12.3 F.12.4 Aqua ad 100 ad 100 ad 100ad 100 Sodium laureth sulfate 35.7 30.0 12.0 Cocamidopropyl betaine 13.515.0 Disodium cocoamphodiacetate 10.0 Sodium cocoamphoacetate 6.0Polysorbate 20 5.0 Decyl glucoside 5.0 1.5 Laureth-3 2.0 Sodium laurethsulfate, glycol 3.0 2.0 distearate, cocamide MEA, laureth-10Coco-glucoside, glyceryl oleate 5.0 Dimethicone 2.0 Conditioning polymer2.0 0.5 0.75 0.4 PUR thickener A.1 0.75 1.2 0.5 1.0 PEG-150 distearate3.0 Citric acid q.s. q.s. Preservative q.s. q.s. q.s. q.s. Fragranceq.s. q.s. q.s. q.s. Dye q.s. q.s. q.s. q.s. Sodium chloride 1.0 1.0

Conditioning polymer is understood as meaning polyquaternium-7, PQ-10,PQ-16, PQ-39, PQ-44, PQ-46, PQ-67, guar hydroxypropyltrimonium chloride,PQ-87, and combinations of these.

Instead of the conditioner shampoo comprising polyurethane thickenerA.1, conditioner shampoos comprising one or more of the polyurethanesA.2, A.3, A.4 and A.5 are also prepared.

Hair Conditioner

Phase Ingredients/INCI F.13.1 F.13.2 F.13.3 F.13.4 F.13.5 A Water ad 100ad 100 ad 100 ad 100 ad 100 PUR thickener 2.5 1.5 3.0 0.6 2.0 A.1Hydroxy- 0.05 0.1 0.2 ethylcellulose Propylene glycol 1.0 2.0 0.8 0.5Panthenol 0.5 0.75 0.25 0.3 B Quaternium-91, 2.0 1.5 cetearyl alcohol,cetrimonium methosulfate Distearoyethyl 3.0 4.0 hydroxy- ethylmoniummethosulfate, cetearyl alcohol Hydrogenated 1.0 1.5 1.0 polyisobuteneCyclo- 2.0 1.0 0.5 pentasiloxane Isopropyl 1.0 2.0 palmitate Persea 2.5Gratissima (Avocado) oil Steareth-2 0.75 0.5 Ceteareth-6, 1.5 0.5stearyl alcohol Ceteareth-25 1.5 Cetearyl alcohol 2.0 1.5 0.5 4.0 CAcrylate/C10-30 0.1 0.2 0.15 alkylacrylate copolymer D Cetrimonium 1.53.0 chloride Conditioning 2.0 6.0 3.0 1.5 0.8 polymer E Preservativeq.s. q.s. q.s. q.s. q.s. Fragrance q.s. q.s. q.s. q.s. q.s.

Conditioning polymer is understood as meaning polyquaternium-7, PQ-10,PQ-16, PQ-39, PQ-44, PQ-46, PQ-67, guar hydroxypropyltrimonium chloride,PQ-87, and combinations of these.

Preparation

Heat phases A and B separately to ca. 80° C.

Stir phase C into phase B, then stir phase A into phase B/C and brieflyhomogenize.

With stirring, cool to ca. 50° C., add components of phase D insuccession and cool to ca. 30° C. with stirring. Add components of phaseE in succession and cool to RT with stirring. Briefly homogenize.

Instead of the hair conditioner comprising polyurethane thickener A.1,hair conditioners comprising one or more of the polyurethanes A.2, A.3,A.4 or A.5 are also prepared.

1. A process for preparing polyurethanes, wherein at least a firstportion of the polyurethanes comprise I) at least two hydrophilicsections S, II) at least one hydrophilic section P different from S,III) at least two terminal hydrophobic sections T, IV) at least twohydrophobic sections D different from T, and wherein a) to each sectionT is directly attached a section S, b) to each section S on at least oneside is attached at least one section D, c) to each section P areattached at least two sections D, and wherein the method comprises usingat least one carboxylic acid salt of at least one metal selected fromthe group consisting of the alkali metals, the alkaline earth metals andmixtures thereof.
 2. The process according to claim 1, wherein at leastsome of the polyurethanes comprise allophanate segments.
 3. The processaccording to at least one of claim 1, wherein at least some of thepolyurethanes comprise isocyanurate segments.
 4. The process accordingto claim 1, further comprising using a solvent, wherein the solvent isnot used to introduce the hydrophilic and hydrophobic sections into thepolyurethanes, and the solvent is in the range from 0 to 10% by weightbased on the reaction mixture.
 5. The process according to claim 1,wherein the process is single-stage.
 6. The process according to claim1, wherein at least a second portion of the polyurethanes comprise I) atleast two hydrophilic sections S, II) no hydrophilic section P, III) atleast two terminal hydrophobic sections T, IV) at least one hydrophobicsection D different from T, where a) to each section T is directlyattached a section S, b) to each section S is attached a section D. 7.The process according to claim 1, wherein the at least one hydrophilicsection P has a number-average molecular weight of from 4000 to 12 000g/mol.
 8. The process according to claim 1, wherein the preparationtakes place in the presence of at least one potassium carboxylate. 9.The process according to claim 1, wherein the preparation takes place inthe presence of less than 10 ppm of tin.
 10. The process according toclaim 6, wherein the preparation takes place in the presence of lessthan 10 ppm of tin.
 11. The process according to claim 1, wherein thepreparation takes place in the presence of less than 10 ppm of zinc. 12.The process according to claim 6, wherein the preparation takes place inthe presence of less than 10 ppm of zinc.
 13. The process according toclaim 1, further comprising using a alkoxylated C₄-C₃₀-alcohol, apolyetherdiol, and a diisocyanate.
 14. The process according to claim13, wherein the at least one C₄-C₃₀-alcohol is a branchedC₁₂-C₃₀-alkanol, the at least one polyetherdiol has a molecular weightM_(n) in the range from 4000 to 12 000 g/mol and the at least onediisocyanate is an aliphatic diisocyanate.
 15. An aqueous preparationcontaining a polyurethane obtained by the process of claim
 1. 16. Acosmetic preparation comprising at least one polyurethane obtained fromthe process of claim 1.